|Número de publicación||US6586529 B2|
|Tipo de publicación||Concesión|
|Número de solicitud||US 09/775,312|
|Fecha de publicación||1 Jul 2003|
|Fecha de presentación||1 Feb 2001|
|Fecha de prioridad||1 Feb 2001|
|También publicado como||DE10291388T0, DE10291388T1, US20020146552, WO2002060497A2, WO2002060497A3|
|Número de publicación||09775312, 775312, US 6586529 B2, US 6586529B2, US-B2-6586529, US6586529 B2, US6586529B2|
|Inventores||Pavneet S. Mumick, Franklin M.C. Chen, Yihua Chang|
|Cesionario original||Kimberly-Clark Worldwide, Inc.|
|Exportar cita||BiBTeX, EndNote, RefMan|
|Citas de patentes (356), Otras citas (24), Citada por (56), Clasificaciones (16), Eventos legales (5)|
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet|
The present invention is directed to water-dispersible polymer formulations. The present invention is also directed to a method of making water-dispersible polymer formulations and their applicability as binder compositions for disposable items. The present invention is further directed to disposable items, such as wet-wipes, comprising water-dispersible binder compositions.
For many years, the problem of disposability has plagued industries that provide disposable items, such as, diapers, wet wipes, incontinent garments and feminine care products. While much headway has been made in addressing this problem, one of the weak links has been the inability to create an economical coherent fibrous web, which will readily dissolve or disintegrate in water, but still have sufficient in-use strength. See, for example, U.K. patent disclosure 2,241,373 and U.S. Pat. No. 4,186,233. Without such a product, the ability of the user to dispose of the product by flushing it down the toilet is greatly reduced, if not eliminated. Furthermore, the ability of the product to disintegrate in a landfill is quite limited because a large portion of the product components, which may well be biodegradable or photodegradable, are encapsulated in or bound together by plastic which degrades over a long period of time, if at all. Accordingly, if the plastic disintegrated in the presence of water, the internal components could degrade as a result of the rupture of the plastic encapsulation or binding.
Disposable products, such as diapers, feminine care products and adult incontinent care products may be made to be disposed by flushing down toilets. Usually such products comprise a body side liner which must rapidly pass fluids, such as urine or menses, so that the fluid may be absorbed by an absorbent core of the product. Typically, the body side liner may be a coherent fibrous web, which desirably possesses a number of characteristics, such as softness and flexibility. The fibrous web of the body side liner material may be typically formed by wet or dry (air) laying a generally random plurality of fibers and joining them together to form a coherent web with a binder compositions. Past binder compositions have performed this function well. However, fibrous webs comprising these compositions tended to be non-dispersible and present problems in typical household sanitation systems.
Recent binder compositions have been developed which can be more dispersible and are more environmentally responsible than past binder compositions. One class of binder compositions includes polymeric materials having inverse solubility in water. These binder compositions are insoluble in warm water, but are soluble in cold water, such as found in a toilet. It is well known that a number of polymers exhibit cloud points or inverse solubility properties in aqueous media. These polymers have been cited in several publications for various applications, including (1) as evaporation retarders (JP 6207162); (2) as temperature sensitive compositions, which are useful as temperature indicators due to a sharp color change associated with a corresponding temperature change (JP 6192527); (3) as heat sensitive materials that are opaque at a specific temperature and become transparent when cooled to below the specific temperature (JP 51003248 and JP 81035703); (4) as wound dressings with good absorbing characteristics and easy removal (JP 6233809); and (5) as materials in flushable personal care products (U.S. Pat. No. 5,509,913, issued to Richard S. Yeo on Apr. 23, 1996 and assigned to Kimberly-Clark Corporation).
Other recent binders of interest include a class of binders, which are ion-sensitive. Several U.S. and European patents assigned to Lion Corporation of Tokyo, Japan, disclose ion-sensitive polymers comprising acrylic acid and alkyl or aryl acrylates. See U.S. Pat. Nos. 5,312,883, 5,317,063 and 5,384,189, the disclosures of which are incorporated herein by reference, as well as, European Pat. No. 608460A1. In U.S. Pat. No. 5,312,883, terpolymers are disclosed as suitable binders for flushable nonwoven webs. The disclosed acrylic acid-based terpolymers, which comprise partially neutralized acrylic acid, butyl acrylate and 2-ethylhexyl acrylate, are suitable binders for use in flushable nonwoven webs in some parts of the world. However, because of the presence of a small amount of sodium acrylate in the partially neutralized terpolymer, these binders fail to disperse in water containing more than about 15 ppm Ca2 + and/or Mg2+. When placed in water containing more than about 15 ppm Ca2 + and/or Mg2 + ions, nonwoven webs using the above-described binders maintain a tensile strength greater than 30 g/in, which negatively affects the “dispersibility” of the web. The proposed mechanism for the failure is that each calcium ion binds with two carboxylate groups either intramolecularly or intermolecularly. Intramolecular association causes the polymer chain to coil up, which eventually leads to polymer precipitation. Intermolecular association yields crosslinking. Whether intramolecular or intermolecular associations are taking place, the terpolymer is not soluble in water containing more than about 15 ppm Ca2 + and/or Mg2 +. Due to the strong interaction between calcium ions and the carboxylate groups of the terpolymer, dissociation of the complex is highly unlikely because this association is irreversible. Therefore, the above described polymer that has been exposed to a high Ca2 + and/or Mg2 + concentration solution will not disperse in water even if the calcium concentration decreases. This limits the application of the polymer as a flushable binder material because most areas across the U.S. have hard water, which contains more than 15 ppm Ca2 + and/or Mg2 +.
In a co-pending application assigned to Kimberly Clark; i.e., U.S. patent application Ser. No. 09/223,999, filed Dec. 31, 1998, the disclosure of which is incorporated herein by reference, there is disclosed a modification of the acrylic acid terpolymers of the above-referenced patents to Lion Corporation. Specifically, U.S. patent application Ser. No. 09/223,999 discloses a sulfonate anion modified acrylic acid terpolymers which has improved dispersibility in relatively hard water; e.g., up to 200 ppm Ca2 + and/or Mg2 +, compared to the unmodified Lion polymers. However, the Lion Corporation ion-sensitive polymers of the above-referenced patents and the sulfonate anion modified acrylic acid terpolymers of the co-pending application, when used as binders for personal care products, such as wet wipes, typically have reduced sheet wettability, increased sheet stiffness, increased sheet stickiness, reduced binder sprayability and relatively high product cost.
Another approach to dispersible personal care products is disclosed in U.S. Pat. No. 5,281,306 to Kao Corporation of Tokyo, Japan (the disclosure of which is incorporated herein by reference). This patent discloses a water-disintegratable cleansing sheet; i.e., wet wipe, comprising water-dispersible fibers treated with a water-soluble polymer binder having a carboxyl group. Examples of water-soluble binders having a carboxyl group include, carboxymethyl cellulose, methacrylic acid-lauryl methacrylate, polyacrylic acid, polymethacrylic acid copolymers of ethyl hexyl acetate, butyl acrylate and acrylic acid, and salts thereof. The cleansing sheet is treated with a cleansing agent containing 5%-95% of a water-compatible organic solvent and 95%-5% water. A preferred organic solvent is propylene glycol. The cleansing sheet does not disperse in the organic solvent-based cleansing agent, but disperses in water. The cleansing sheet also includes a metallic ion selected from alkaline earth metals, such as magnesium, calcium, strontium, barium, manganese, zinc, cobalt and nickel. Although the Kao patent indicates that all polymers containing carboxyl groups maintain wet strength, not all polymers so disclosed, such as polyacrylic acid and salts thereof, satisfactorily maintain wet strength.
Although many patents disclose various ion and temperature sensitive compositions for water-dispersible or flushable materials, there exists a need for dispersible products possessing softness, flexibility, three dimensionality, and resiliency; wicking and structural integrity in the presence of body fluids (including feces) at body temperature; and true fiber dispersion after toilet flushing so that fibers do not become entangled with tree roots or at bends in sewer pipes. In addition, the known ion-sensitive polymers, such as those of Lion Corporation and the co-pending application of Kimberly Clark, have relatively high viscosities at high shear rates that make application by spraying impossible or impractical. Moreover, there is a need in the art for flushable products having water-dispersibility in all areas of the world, including soft and hard water areas. Furthermore, there is a need for water-dispersible binders that do not reduce wettability of product with which they are used and are sprayable for easy and uniform application to and penetration into products.
The present invention is directed to polymer formulations, which have been developed to address the above-described problems associated with currently available, water-dispersible polymers and other polymers described in literature. The polymer formulations of the present invention are insoluble in a wetting composition comprising 5%-95% of a water-compatible organic solvent and 95%-5% water, but is soluble in water, including water containing divalent salt solutions, such as hard water with up to 200 ppm (parts per million) calcium and magnesium ions. Unlike some water-dispersible polymer binder formulations which lose wet strength, the polymer formulations of the present invention retain significant wet strength. Consequently, flushable products containing the polymer formulations of the present invention maintain strength when wetted with a wetting solution, but are dispersibility in hard water. Furthermore, the polymer formulations of the present invention have improved properties of sprayability.
The polymer formulations of the present invention are useful as binders and structural components for air-laid and wet-laid nonwoven fabrics for applications such as body-side liners, fluid distribution materials, fluid in-take materials (surge) or cover stock in various personal care products. The polymer formulations of the present invention are particularly useful as a binder material for flushable personal care products, particularly wet wipes for personal use such as cleaning or treating skin, makeup removal, nail polish removal, medical care, and also wipes for use in hard surface deaning, automotive care, including wipes comprising cleaning agents, disinfectants, and the like. The flushable products maintain integrity or wet strength during storage and use, and break apart or disperse after disposal in the toilet when the organic solvent concentration falls below a critical level. Suitable substrates for treatment include tissue, such as creped or uncreped tissue, coform products, hydroentangled webs, airlaid mats, fluff pulp, nonwoven webs, and composites thereof. Methods for producing uncreped tissues and molded three-dimensional tissue webs of use in the present invention can be found in commonly owned U.S. patent application, Ser. No. 08/912,906, “Wet Resilient Webs and Disposable Articles Made Therewith,” by F. -J. Chen et al., filed Aug. 15, 1997; U.S. Pat. No. 5,429,686, issued to Chiu et al. on Jul. 4, 1995; U.S. Pat. No. 5,399,412, issued to S. J. Sudall and S. A. Engel on Mar. 21, 1995; U.S. Pat. No. 5,672,248, issued to Wendtet al. on Sept. 30, 1997; and U.S. Pat. No. 5,607,551, issued to Farrington et al. on Mar. 4, 1997; all of which are herein incorporated in their entirety by reference. The molded tissue structures of the above patents can be especially helpful in providing good cleaning in a wet wipe. Good cleaning can also be promoted by providing a degree of texture in other substrates as well by embossing, molding, wetting and through-air drying on a textured fabric, and the like.
Airlaid material can be formed by metering an airflow containing the fibers and other optional materials, in substantially dry condition, onto a typically horizontally moving wire forming screen. Suitable systems and apparatus for air-laying mixtures of fibers and thermoplastic material are disclosed in, for example, U.S. Pat. No. 4,157,724 (Persson), issued Jun. 12, 1979, and reissued Dec. 25, 1984 as Re. U.S. Pat. No. 31,775; U.S. Pat. No. 4,278,113 (Persson), issued Jul. 14, 1981; U.S. Pat. No. 4,264,289 (Day), issued Apr. 28, 1981; U.S. Pat. No. 4,352,649 (Jacobsen et al.), issued Oct. 5, 1982; U.S. Pat. No. 4,353,687 (Hosler, et al.), issued Oct. 12, 1982; U.S. Pat. No. 4,494,278 (Kroyer, et al.), issued Jan. 22, 1985; U.S. Pat. No. 4,627,806 (Johnson), issued Dec. 9, 1986; U.S. Pat. No. 4,650,409 (Nistri, et al.), issued Mar. 17, 1987; and U.S. Pat. No. 4,724,980 (Farley), issued Feb. 16, 1988; and U.S. Pat. No. 4,640,810 (Laursen et al.), issued Feb. 3, 1987.
The present invention also discloses how to make water-dispersible nonwovens, including cover stock (liner), intake (surge) materials and wet wipes, which are stable in fluids having 5%-95% of a water-compatible organic solvent and 95%-5% water, using the above-described unique polymer formulations as binder compositions. The resultant nonwovens are flushable and water-dispersible due to the water dispersibility of the binder. The polymer formulations with which such articles are treated can have improved properties of sprayability, which improves polymer distribution on the product and penetration into the product, in addition to ease of application, which translates into cost savings.
These and other objects, features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended drawing and claims.
In order to be an effective polymer formulation suitable for use in flushable or water-dispersible personal care products, the formulations should desirably be (1) functional; i.e., maintain wet strength under controlled conditions and dissolve or disperse rapidly in soft or hard water such as found in toilets and sinks around the world; (2) safe (not toxic); and (3) relatively economical. In addition to the foregoing factors, the polymer formulations when used as a binder composition for a non-woven substrate, such as a wet wipe, desirably should be (4) processable on a commercial basis; i.e., may be applied relatively quickly on a large scale basis, such as by spraying, which thereby requires that the binder composition have a relatively low viscosity at high shear; and (5) provide acceptable levels of sheet or substrate wettability. The wetting composition with which the wet wipes of the present invention are treated can provide some of the foregoing advantages, and, in addition, can provide (6) improved skin care, such as reduced skin irritation or other benefits. The polymer formulations of the present invention and articles made therewith, especially wet wipes comprising particular wetting compositions set forth below, can meet many or all of the above criteria. Of course, it is not necessary for all of the advantages of the preferred embodiments of the present invention to be met to fall within the scope of the present invention.
The polymer formulations of the present invention are formed from a blend of two polymers. One of the polymers of the polymer formulations of the present invention is a synthetic water-soluble polymer. Water-soluble polymers useful in the present invention include water-soluble polymer containing carboxylate groups which also have flexible polymer chains. Such water-soluble polymers are disclosed in U.S. Pat. No. 5,281,306, the disclosure of which is incorporated herein by reference in its entirety. A useful water-soluble polymer is sodium polyacrylate. A sodium polyacrylate useful in the present invention is commercially available under the designation NS 9893-92A and NS 9893-92B from National Starch and Chemical Co., Bridgewater, N.J.
Water-soluble acrylic acid copolymers useful in the present invention may comprise any combination of acrylic acid monomers and acrylic ester (alkyl acrylate) monomers capable of free radical polymerization into a copolymer. Suitable acrylic acid monomers include, but are not limited to, acrylic acid and methacrylic acid. Suitable acrylic monomers include, but are not limited to, acrylic esters and methacrylic esters having an alkyl group of 1 to 18 carbon atoms or a cycloalkyl group of 3 to 18 carbonatoms and it is preferred that acrylic esters and/or methacrylic esters having an alkyl group of 1 to 12 carbon atoms or a cycloalkyl group of 3 to 12 carbon atoms may be used singly or in combination.
The relative amounts of the monomers in the acrylic acid copolymer of the present invention may vary depending on the desired properties in the resulting polymer. The mole percent of acrylic acid monomer in the copolymer is up to about 70 mole percent. More specifically, the mole percent of acrylic acid monomer in the copolymer is from about 15 to about 50 mole percent. Most specifically, the mole percent of acrylic acid monomer in the copolymer is from about 25 to about 40 mole percent.
More specifically, examples of the acrylic acid copolymers useful in the present invention include copolymers of 10 weight percent to 90 weight percent, desirably 20 weight percent to 70 weight percent of acrylic acid and/or methacrylic acid and 90 weight percent to 10 weight percent, desirably 80 weight percent to 30 weight percent of acrylic esters and/or methacrylic esters having an alkyl group of 1 to 18 carbon atoms or a cycloalkyl group of 3 to 18 carbon atoms in which 1 to 60 mole percent, desirably 5 to 50 mole percent of acrylic acid and/or methacrylic acid is neutralized to form a salt; or copolymers of 30 weight percent to 75 weight percent, desirably 40 weight percent to 65 weight percent of acrylic acid, 5 weight percent to 30 weight percent, desirably 10 weight percent to 25 weight percent of acrylic esters and/or methacrylic esters having an alkyl group of 8 to 12 carbon atoms and 20 weight percent to 40 weight percent; desirably 25 weight percent to 35 weight percent of acrylic esters and/or methacrylic esters having an alkyl group of 2 to 4 carbon atoms in which 1 to 50 mole percent, desirably 2 to 40 mole percent of acrylic acid is neutralized to form a salt.
The acrylic acid copolymers of the present invention may have an average molecular weight, which varies depending on the ultimate use of the polymer. The acrylic acid copolymers of the present invention have a weight average molecular weight ranging from about 10,000 to about 5,000,000. More specifically, the acrylic acid copolymers of the present invention have a weight average molecular weight ranging from about 25,000 to about 2,000,000, or, more specifically still, from about 200,000 to about 1,000,000.
The acrylic acid copolymers of the present invention may be prepared according to a variety of polymerization methods, desirably a solution polymerization method. Suitable solvents for the polymerization method include, but are not limited to, lower alcohols such as methanol, ethanol and propanol; a mixed solvent of water and one or more lower alcohols mentioned above; and a mixed solvent of water and one or more lower ketones such as acetone or methyl ethyl ketone.
In the polymerization methods of the present invention, any polymerization initiator may be used. Selection of a particular initiator may depend on a number of factors including, but not limited to, the polymerization temperature, the solvent, and the monomers used. Suitable polymerization initiators for use in the present invention include, but are not limited to, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutylamidine), potassium persulfate, ammonium persulfate, and aqueous hydrogen peroxide. The amount of polymerization initiator may desirably range from about 0.01 to 5 weight percent based on the total weight of monomer present.
The polymerization temperature may vary depending on the polymerization solvent, monomers, and initiator used, but in general, ranges from about 20° C. to about 90° C. Polymerization time generally ranges from about 2 to about 8 hours.
If polyacrylic acid is used as one of the monomers, it is desired to neutralize at least a portion of the acid component. Any inorganic base or organic base may be used as a neutralizing agent to neutralize the acid component. Examples of neutralizing agents include, but are not limited to, inorganic bases, such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium carbonate, and amines, such as monoethanolamine, diethanolamine, diethylaminoethanol, ammonia, trimethylamine, triethylamine, tripropylamine, morpholine. Preferred neutralizing agents include sodium hydroxide, potassium hydroxide, or a combination thereof.
In a further embodiment of the present invention, the above-described water-soluble polymer formulations are used as binder materials for flushable and/or non-flushable products. In order to be effective as a binder material in flushable products throughout the United States, the ion-sensitive polymer formulations of the present invention remain stable and maintain their integrity while dry or in a wetting composition comprising 5%-95% of a water-compatible organic solvent and 95%-5% water, but is soluble in water, including water containing divalent salt solutions, such as hard water with up to 200 ppm (parts per million) calcium and magnesium ions. Desirably, the ion-sensitive polymer formulations of the present invention including acrylic acid copolymers are insoluble in a composition comprising 20% water-compatible organic solvent and 80% water.
As stated above, the polymer formulations of the present invention are formed from a combination of two or more different polymers, wherein at least one polymer is water-soluble polymer. The second polymer is an emulsion polymer. Furthermore, the emulsion polymer may be insoluble in water and can reduce the shear viscosity of the water-soluble polymer. Examples of emulsion polymers useful in the present invention include, but are not limited to, styrene acrylic emulsions and styrenebutadiene emulsions. Styrene emulsions useful in the present invention are commercially available under the designation Rhoplex P-308 and Rhoplex NW-1715K from Rohm and Haas, Philadelphia, Pa. Styrene-butadiene emulsions useful in the present invention are commercially available under the designation Rovene 4470, Rovene 4457 and Rovene 4817 from Mallard Creek Polymers, Charlotte, N.C.
In the polymer blend of the present invention, the water-soluble polymer is present in an amount of approximately 50% to 95% by weight and the emulsion polymer is present in an amount of approximately 5% to 50% by weight. Desirable, the water-soluble polymer is present in an amount of approximately 70% to 90% by weight and the emulsion polymer is present in an amount of approximately 10% to 30% by weight.
In blending the water-soluble polymer and the emulsion polymer, the sequence of blending is important. One must avoid procedures that could shock the surfactant systems of the emulsion polymers. The procedure followed in the present invention is to initially dilute the water-soluble polymer with water. Then, while stirring the diluted water-soluble polymer, the emulsion polymer is slowly added to the water-soluble polymer.
Desirably, but not necessarily, the emulsion polymer when combined with the water-soluble polymer will reduce the shear viscosity of the water-soluble polymer to such an extent that the combination of the water-soluble polymer and the emulsion polymer is sprayable. By sprayable is meant that the polymer can be applied to a nonwoven fibrous substrate by spraying and the distribution of the polymer across the substrate and the penetration of the polymer into the substrate are such that the polymer formulation is uniformly applied to the substrate.
The co-binder polymer can be in the form of an emulsion latex. The surfactant system used in such a latex emulsion should be such that it does not substantially interfere with the dispersibility of the water-soluble polymer.
The emulsion polymer of the present invention can have an average molecular weight, which varies depending on the ultimate use of the polymer. Desirably, the emulsion polymer has a weight average molecular weight ranging from about 500,000 to about 200,000,000. More desirably, the emulsion polymer has a weight average molecular weight ranging from about 500,000 to about 100,000,000.
Emulsion polymers that can meet many or all of the foregoing criteria include, but are not limited to, poly(ethylene-vinyl acetate), poly(styrene-butadiene), poly(styrene-acrylic), a vinyl acrylic terpolymer, neoprene, a polyester latex, an acrylic emulsion latex, poly vinyl chloride, ethylene-vinyl chloride copolymer, a carboxylated vinyl acetate latex, and the like. A particularly preferred poly(styrene-butadiene) is Rovene® 4817 available from Mallard Creek Polymers, Charlotte, N.C. A particularly preferred poly(styrene-acrylic) is Rhoplex® NM 1715K available from Rohm and Haas, Philadelphia, Pa.
As stated above, useful emulsion polymers can include a variety of commercial latex emulsions, including those selected from the Rovene® series (styrene butadiene latices available from Mallard Creek Polymers of Charlotte, N.C.), the Rhoplex® latices of Rohm and Haas Company, and the Elite® latices of National Starch. Polymer emulsions or dispersions generally comprise small polymer particles, such as crosslinkable ethylene vinyl acetate copolymers, typically in spherical form, dispersed in water and stabilized with surface active ingredients, such as low molecular weight emulsifiers or high molecular weight protective colloids. These liquid binders can be applied to airlaid webs or other substrates by methods known in the art of binder treatment for nonwoven webs, including spray or foam application, flooded nip impregnation, curtain coating, etc., followed by drying. In general, a wide variety of latex compounds and other resins or emulsions can be considered, including vinyl acetate copolymer latices, such as 76 RES 7800 from Union Oil Chemicals Divisions and Resyn® 25-1103, Resyn® 25-1109, Resyn® 25-1119, and Resyn® 25-1189 from National Starch and Chemical Corporation, ethylene-vinyl acetate copolymer emulsions, such as Airflex® ethylene-vinylacetate from Air Products and Chemicals Inc., acrylic-vinyl acetate copolymer emulsions, such as Rhoplex® AR-74 from Rohm and Haas Company, Synthemul® 97-726 from Reichhold Chemicals Inc., Resyn® 25-1140, 25-1141, 25-1142, and Resyn-6820 from National Starch and Chemical Corporation, vinyl acrylic terpolymer latices, such as 76 RES 3103 from Union Oil Chemical Division, and Resyn® 251110 from National Starch and Chemical Corporation, acrylic emulsion latices, such as Rhoplex® B-15J, Rhoplex® P-376, Rhoplex® TR-407, Rhoplex® E-940, Rhoplex® TR934, Rhoplex® TR-520, Rhoplex® HA-24, and Rhoplex® NW1825 from Rohm and Haas Company, and Hycar® 2600×322, Hycar® 2671, Hycar® 2679, Hycar® 26120, and Hycar® 2600×347 from B. F. Goodrich Chemical Group, styrene-butadiene latices, such as 76 RES 4100 and 76 RES 8100 available from Union Oil Chemicals Division, Tylac® resin emulsion 68-412, Tylac® resin emulsion 68-067, 68-319, 68-413, 68-500, 68-501, available from Reichhold Chemical Inc., and DL6672A, DL6663A, DL6638A, DL6626A, DL6620A, DL615A, DL617A, DL620A, DL640A, DL650A available from Dow Chemical Company; and rubber latices, such as neoprene available from Serva Biochemicals; polyester latices, such as Eastman AQ 29D available from Eastman Chemical Company; vinyl chloride latices, such as Geon® 352 from B. F. Goodrich Chemical Group; ethylene-vinyl chloride copolymer emulsions, such as Airflex® ethylene-vinyl chloride from Air Products and Chemicals; polyvinyl acetate homopolymer emulsions, such as Vinac® from Air Products and Chemicals; carboxylated vinyl acetate emulsion resins, such as Synthemul® synthetic resin emulsions 40-502, 40-503, and 97-664 from Reichhold Chemicals Inc. and Polyco® 2149, 2150, and 2171 from Rohm and Haas Company. Silicone emulsions can also be considered.
Polymer Formulations and Fabrics Containing the Same
The polymer formulations of the present invention may be used as binders. The binder formulations of the present invention may be applied to any fibrous substrate. The binders are particularly suitable for use in water-dispersible products. Suitable fibrous substrates include, but are not limited to, nonwoven and woven fabrics. In many embodiments, particularly personal care products, preferred substrates are nonwoven fabrics. As used herein, the term “nonwoven fabric” refers to a fabric that has a structure of individual fibers or filaments randomly arranged in a mat-like fashion (including papers). Nonwoven fabrics can be made from a variety of processes including, but not limited to, air-laid processes, wet-laid processes, hydroentangling processes, staple fiber carding and bonding, and solution spinning.
The binder composition may be applied to the fibrous substrate by any known process of application. Suitable processes for applying the binder material include, but are not limited to, printing, spraying, electrostatic spraying, coating, flooded nips, metered press rolls, impregnating or by any other technique. The amount of binder composition may be metered and distributed uniformly within the fibrous substrate or may be non-uniformly distributed within the fibrous substrate. The binder composition may be distributed throughout the entire fibrous substrate or it may be distributed within a multiplicity of small closely spaced areas. In most embodiments, uniform distribution of binder composition is desired.
For ease of application to the fibrous substrate, the binder may be dissolved in water, or in a non-aqueous solvent, such as methanol, ethanol, acetone, or the like, with water being the preferred solvent. The amount of binder dissolved in the solvent may vary depending on the polymer used and the fabric application. Desirably, the binder solution contains up to about 25 percent by weight of binder composition solids. More desirably, the binder solution contains from about 10 to 20 percent by weight of binder composition solids, especially about 12 percent by weight binder composition solids. Plasticizers, perfumes, coloring agents, antifoams, bactericides, preservative, surface active agents, thickening agents, fillers, opacifiers, tackifiers, detackifiers, and similar additives can be incorporated into the solution of binder components, if so desired.
Once the binder composition is applied to the substrate, the substrate is dried by any conventional means. Once dry, the coherent fibrous substrate exhibits improved tensile strength when compared to the tensile strength of the untreated wet-laid or dry-laid substrates, and yet has the ability to rapidly “fall apart”, or disintegrate when placed in soft or hard water having a relatively high multivalent ionic concentration and agitated. For example, the dry tensile strength of the fibrous substrate may be increased by at least 25 percent as compared to the dry tensile strength of the untreated substrate not containing the binder. More particularly, the dry tensile strength of the fibrous substrate may be increase by at least 100 percent as compared to the dry tensile strength of the untreated substrate not containing the binder. Even more particularly, the dry tensile strength of the fibrous substrate may be increased by at least 500 percent as compared to the dry tensile strength of the untreated substrate not containing the binder.
A desirable feature of the present invention is that the improvement in tensile strength is effected where the amount of binder composition present, “add-on”, in the resultant fibrous substrate represents only a small portion by weight of the entire substrate. The amount of “add-on” can vary for a particular application; however, the optimum amount of “add-on” results in a fibrous substrate which has integrity while in use and also quickly disperses when agitated in water. For example, the binder components typically are from about 5 to about 65 percent, by weight, of the total weight of the substrate. More particularly, the binder components may be from about 10 to about 35 percent, by weight, of the total weight of the substrate. Even more particularly, the binder components may be from about 17 to about 22 percent by weight of the total weight of the substrate.
The nonwoven fabrics of the present invention have good in-use tensile strength. Desirably, the nonwoven fabrics of the present invention are abrasion resistant and retain significant tensile strength in aqueous solutions containing greater than about 0.5 weight percent water-compatible organic solvent. Yet, the nonwoven fabrics are dispersible in very soft to moderately hard to hard water. Because of this latter property, nonwoven fabrics of the present invention are well suited for disposable products, such as pre-moistened wipes (wet wipes), which can be thrown in a flush toilet after use in any part of the world.
The fibers forming the fabrics above can be made from a variety of materials including natural fibers, synthetic fibers, and combinations thereof. The choice of fibers depends upon, for example, the intended end use of the finished fabric and fiber cost. For instance, suitable fibrous substrates may include, but are not limited to, natural fibers such as cotton, linen, jute, hemp, wool, wood pulp, etc. Similarly, regenerated cellulosic fibers, such as viscose rayon and cuprammonium rayon, modified cellulosic fibers, such as cellulose acetate, or synthetic fibers, such as those derived from polypropylenes, polyethylenes, polyolefins, polyesters, polyamides, polyacrylics, etc., alone or in combination with one another, may likewise be used. Blends of one or more of the above fibers may also beused, if so desired. Among wood pulp fibers, any known papermaking fibers may be used, including softwood and hardwood fibers. Fibers, for example, may be chemically pulped or mechanically pulped, bleached or unbleached, virgin or recycled, high yield or low yield, and the like. Mercerized, chemically stiffened or crosslinked fibers may also be used.
Synthetic cellulose fiber types include rayon in all its varieties and other fibers derived from viscose or chemically modified cellulose, including regenerated cellulose and solvent-spun cellulose, such as Lyocell. Chemically treated natural cellulosic fibers can be used, such as mercerized pulps, chemically stiffened or crosslinked fibers, or sulfonated fibers. Recycled fibers, as well as virgin fibers, can be used. Cellulose produced by microbes and other cellulosic derivatives can be used. As used herein, the term “cellulosic” is meant to include any material having cellulose as a major constituent, and, specifically, comprising at least 50 percent by weight cellulose or a cellulose derivative. Thus, the term includes cotton, typical wood pulps, non-woody cellulosic fibers, cellulose acetate, cellulose triacetate, rayon, thermomechanical wood pulp, chemical wood pulp, debonded chemical wood pulp, milkweed, or bacterial cellulose. The fiber length is important in producing the fabrics of the present invention. In some embodiments, such as flushable products, fiber length is of more importance. The minimum length of the fibers depends on the method selected for forming the fibrous substrate. For example, where the fibrous substrate is formed by carding, the length of the fiber should usually be at least about 42 mm in order to insure uniformity. Where the fibrous substrate is formed by air-laid or wet-laid processes, the fiber length may desirably be about 0.2 to 6 mm. Although fibers having a length of greater than 50 mm are within the scope of the present invention, it has been determined that when a substantial quantity of fibers having a length greater than about 15 mm is placed in a flushable fabric, though the fibers will disperse and separate in water, their length tends to form “ropes” of fibers, which are undesirable when flushing in home toilets. Therefore, for these products, it is desired that the fiber length be about 15 mm or less so that the fibers will not have a tendency to “rope” when they are flushed through a toilet. Although fibers of various lengths are applicable in the present invention, desirably fibers are of a length less than about 15 mm so that the fibers disperse easily from one another when in contact with water. The fibers, particularly synthetic fibers, can also be crimped The fabrics of the present invention may be formed from a single layer or multiple layers. In the case of multiple layers, the layers are generally positioned in a juxtaposed or surface-to-surface relationship and all or a portion of the layers may be bound to adjacent layers. Nonwoven webs of the present invention may also be formed from a plurality of separate nonwoven webs wherein the separate nonwoven webs may be formed from single or multiple layers. In those instances where the nonwoven web includes multiple layers, the entire thickness of the nonwoven web may be subjected to a binder application or each individual layer may be separately subjected to a binder application and then combined with other layers in a juxtaposed relationship to form the finished nonwoven web.
In one embodiment, the fabric substrates of the present invention may be incorporated into cleansing and body fluid absorbent products, such as sanitary napkins, diapers, adult incontinence products, surgical dressings, tissues, wet wipes, and the like. These products may include an absorbent core, comprising one or more layers of an absorbent fibrous material. The core may also comprise one or more layers of a fluid-pervious element, such as fibrous tissue, gauze, plastic netting, etc. These are generally useful as wrapping materials to hold the components of the core together. Additionally, the core may comprise a fluid-impervious element or barrier means to preclude the passage of fluid through the core and on the outer surfaces of the product. Desirably, the barrier means also is water-dispersible. A film of a polymer having substantially the same composition as the aforesaid water-dispersible binder is particularly well-suited for this purpose. In accordance with the present invention, the polymer compositions are useful for forming each of the above-mentioned product components including the layers of absorbent core, the fluid-pervious element, the wrapping materials, and the fluid-impervious element or barrier means.
The binder formulations of the present invention are particularly useful for binding fibers of air-laid nonwoven fabrics. These air-laid materials are useful for body-side liners, fluid distribution materials, fluid in-take materials, such as a surge material, absorbent wrap sheet and cover stock for various water-dispersible personal care products. Air-laid materials are particularly useful for use as a pre-moistened wipe (wet wipe). The basis weights for air-laid non-woven fabrics may range from about 20 to about 200 grams per square meter (“gsm”) with staple fibers having a denier of about 0.5-10 and a length of about 6-15 millimeters. Surge, or in-take, materials need better resiliency and higher loft so staple fibers having about 6 denier or greater are used to make these products. A desirable final density for the surge, or in-take, materials is between about 0.025 grams per cubic centimeter (“g/cc”) to about 0.10 g/cc. Fluid distribution materials may have a higher density, in the desired range of about 0.10 to about 0.20 g/cc using fibers of lower denier, most desirable fibers have a denier of less than about 1.5. Wipes generally can have a fiber density of about 0.025 g/cc to about 0.2 g/cc and a basis weight of about 20 gsm to about 150 gsm; specifically from about 30 to about 90 gsm, and most specifically from about 60 gsm to about 65 gsm.
Unlike other binder systems known in the art, the polymer formulations of the present invention can be activated as binders without the need for elevated temperature. While drying or water removal is useful in achieving a good distribution of the binder in a fibrous web, elevated temperature, per se, is not essential because the binder does not require crosslinking or other chemical reactions with high activation energy to serve as a binder. Rather, the interaction with a soluble activating compound, typically a water-compatible organic solvent, is sufficient to cause the binder to become active (insoluble). Thus, a drying step can be avoided, if desired, or replaced with low-temperature water removal operations, such as room-temperature drying or freeze drying. Elevated temperature is generally helpful for drying, but the drying can be done at temperatures below what is normally needed to drive crosslinking reactions. Thus, the peak temperature to which the substrate is exposed or to which the substrate is brought can be below any of the following: 180° C., 160° C., 140° C., 120° C., 110° C., 105° C., 100° C., 90° C., 75° C., and 60° C., with an exemplary range for peak web temperature of from about 50° C. to about 110° C., or from about 70° C. to about 140° C. Of course, higher temperatures can be used, but are not necessary in most embodiments. While polymer systems, such as commercial latex emulsions, may also comprise crosslinkers suited for reaction at temperatures of 160° C. or higher, maintaining a lower peak temperature can be beneficial in preventing development of excessive strength in the polymer that might otherwise hinder the water dispersibility of the pre-moistened wipe.
Wet Wipe Wetting Composition and Wet Wipes Containing the Same
One particularly interesting embodiment of the present invention is the production of pre-moistened wipes, or wet wipes, from the above-described binder compositions and fibrous materials. For wipes, the fibrous material may be in the form of a woven or nonwoven fabric; however, nonwoven fabrics are more desirable. The nonwoven fabric is, desirably, formed from relatively short fibers, such as wood pulp fibers. The minimum length of the fibers depends on the method selected for forming the nonwoven fabric. Where the nonwoven fabric is formed by a wet or dry method, the fiber length is desirably from about 0.1 millimeters to 15 millimeters. Desirably, the nonwoven fabric of the present invention has a relatively low wet cohesive strength when it is not bonded together by an adhesive or binder material. When such nonwoven fabrics are bonded together by a binder composition, which loses its bonding strength in tap water and in sewer water, the fabric will break up readily by the agitation provided by flushing and moving through the sewer pipes.
The finished wipes may be individually packaged, desirably in a folded condition, in a moisture proof envelope or packaged in containers holding any desired number of sheets in a water-tight package with a wetting composition applied to the wipe. The finished wipes may also be packaged as a roll of separable sheets in a moisture-proof container holding any desired number of sheets on the roll with a wetting composition applied to the wipes. The roll can be coreless and either hollow or solid. Coreless rolls, including rolls with a hollow center or without a solid center, can be produced with known coreless roll winders, including those of SRP Industry, Inc. (San Jose, Calif.); Shimizu Manufacturing (Japan), and the devices disclosed in U.S. Pat. No. 4,667,890, issued May 26, 1987 to Gietman. Solid-wound coreless rolls can offer more product for a given volume and can be adapted for a wide variety of dispensers.
Relative to the weight of the dry fabric, the wipe may desirably contain from about 10 percent to about 400 percent of the wetting composition, more desirably from about 100 percent to about 300 percent of the wetting composition, and even more desirably from about 180 percent to about 240 percent of the wetting composition. The wipe maintains its desired characteristics over the time periods involved in warehousing, transportation, retail display and storage by the consumer. Accordingly, shelf life may range from two months to two years.
Various forms of impermeable envelopes and storage means for containing wet-packaged materials, such as wipes and towelettes and the like, are well known in the art. Any of these may be employed in packaging the pre-moistened wipes of the present invention.
Desirably, the pre-moistened wipes of the present invention are wetted with an aqueous wetting composition, which has one or more of the following properties:
(1) is compatible with the above-described binder compositions of the present invention;
(2) enables the pre-moistened wipe to maintain its wet strength during converting, storage and usage (including dispensing), as well as, dispersibility in a toilet bowl;
(3) does not cause skin irritation;
(4) reduces tackiness of the wipe, and provides unique tactile properties, such as skin glide and a “lotion-like feel”; and
(5) acts as a vehicle to deliver “moist cleansing” and other skin health benefits.
The wetting composition should not act as a solvent for the binder. However, the wetting composition should contain an amount of a water-compatible organic solvent that preserves the wet strength of the wet wipe. Desirably, the wetting composition contains 5%-95% of a water-compatible organic solvent and 95%-5% water. A preferred organic solvent is propylene glycol.
The wetting composition of the present invention may further comprise a variety of additives compatible with the water-compatible organic solvent and the water-dispersible binder, such that the strength and dispersibility functions of the wipe are not jeopardized. Suitable additives in the wetting composition include, but are not limited to, the following additives: skin-care additives; odor control agents; particulates; antimicrobial agents; preservatives; wetting agents and cleaning agents, such as detergents, surfactants, and some silicones; emollients; surface feel modifiers for improved tactile sensation (e.g., lubricity) on the skin; fragrance; fragrance solubilizers; opacifiers; fluorescent whitening agents; UV absorbers; pharmaceuticals; and pH control agents, such as malic acid or potassium hydroxide.
As used herein, the term “skin-care additives” represents additives, which provide one or more benefits to the user, such as a reduction in the probability of having diaper rash and/or other skin damage caused by fecal enzymes. These enzymes, particularly trypsin, chymotrypsin and elastase, are proteolytic enzymes produced in the gastrointestinal tract to digest food. In infants, for example, the feces tend to be watery and contain, among other materials, bacteria, and some amounts of undegraded digestive enzymes. These enzymes, if they remain in contact with the skin for any appreciable period of time, have been found to cause an irritation that is uncomfortable in itself and can predispose the skin to infection by microorganisms. As a countermeasure, skin-care additives include, but are not limited to, the enzyme inhibitors and sequestrants set forth hereafter. The wetting composition may contain less than about 5 weight percent of skin-care additives based on the total weight of the wetting composition. More specifically, the wetting composition may contain from about 0.01 weight percent to about 2 weight percent of skin-care additives. Even more specifically, the wetting composition may contain from about 0.01 weight percent to about 0.05 weight percent of skin-care additives.
A variety of skin-care additives may be added to the wetting composition and the pre-moistened wipes of the present invention or included therein. In one embodiment of the present invention, skin-care additives in the form of particles are added to serve as fecal enzyme inhibitors, offering potential benefits in the reduction of diaper rash and skin damage caused by fecal enzymes. U.S. Pat. No. 6,051,749, issued Apr. 18, 2000 to Schulz et al., the entirety of which is herein incorporated by reference, discloses organophilic clays in a woven or nonwoven web, said to be useful for inhibiting fecal enzymes. Such materials may be used in the present invention, including reaction products of a long chain organic quaternary ammonium compound with one or more of the following clays: montmorillonite, bentonite, beidellite, hectorite, saponite, and stevensite.
Other known enzyme inhibitors and sequestrants may be used as skin-care additives in the wetting composition of the present invention, including those that inhibit trypsin and other digestive or fecal enzymes, and inhibitors for urease. For example, enzyme inhibitors and anti-microbial agents may be used to prevent the formation of odors in body fluids. For example, urease inhibitors, which are also said to play a role in odor absorption, are disclosed by T. Trinh in World Patent Application No. 98/26808, “Absorbent Articles with Odor Control System,” published Jun. 25, 1998, the entirety of which is herein incorporated by reference. Such inhibitors may be incorporated into the wetting composition and the pre-moistened wipes of the present invention and include transition metal ions and their soluble salts, such as silver, copper, zinc, ferric, and aluminum salts. The anion may also provide urease inhibition, such as borate, phytate, etc. Compounds of potential value include, but are not limited to, silver chlorate, silver nitrate, mercury acetate, mercury chloride, mercury nitrate, copper metaborate, copper bromate, copper bromide, copper chloride, copper dichromate, copper nitrate, copper salicylate, copper sulfate, zinc acetate, zinc borate, zinc phytate, zinc bromate, zinc bromide, zinc chlorate, zinc chloride, zinc sulfate, cadmium acetate, cadmium borate, cadmium bromide, cadmium chlorate, cadmium chloride, cadmium formate, cadmium iodate, cadmium iodide, cadmium permanganate, cadmium nitrate, cadmium sulfate, and gold chloride.
Other salts that have been disclosed as having urease inhibition properties include ferric and aluminum salts, especially the nitrates, and bismuth salts. Other urease inhibitors are disclosed by Trinh, including hydroxamic acid and its derivatives; thiourea; hydroxylamine; salts of phytic acid; extracts of plants of various species, including various tannins, e.g. carob tannin, and their derivatives such as chlorogenic acid derivatives; naturally occurring acids such as ascorbic acid, citric acid, and their salts; phenyl phosphoro diamidate/diamino phosphoric acid phenyl ester; metal aryl phosphoramidate complexes, including substituted phosphorodiamidate compounds; phosphoramidates without substitution on the nitrogen; boric acid and/or its salts, including especially, borax, and/or organic boron acid compounds; the compounds disclosed in European Patent Application 408,199; sodium, copper, manganese, and/or zinc dithiocarbamate; quinones; phenols; thiurams; substituted rhodanine acetic acids; alkylated benzoquinones; formarnidine disulphide; 1:3-diketones maleic anhydride; succinamide; phthalic anhydride; pehenic acid; /N,N-dihalo-2-imidazolidinones; N-halo2-oxazolidinones; thio- and/or acyl-phosphoryltnamide and/or substituted derivatives thereof-, thiopyridine-N-oxides, thiopyridines, and thiopyrimidines; oxidized sulfur derivatives of diarninophosphinyl compounds; cyclotriphosphazatriene derivatives; ortho-diaminophosphinyl derivatives of oximes; bromo-nitro compounds; S-aryl and/or alkyl diamidophosphorothiolates; diaminophosphinyl derivatives; mono- and/or polyphosphorodiamide; 5-substituted-benzoxathiol-2-ones; N(diaminophosphinyl)arylcarboxamides; alkoxy-1,2-benzothaizin compounds; etc.
Many other skin-care additives may be incorporated into the wetting composition and pre-moistened wipes of the present invention, including, but not limited to, sun blocking agents and UV absorbers, acne treatments, pharmaceuticals, baking soda (including encapsulated forms thereof), vitamins and their derivatives such as Vitamins A or E, botanicals such as witch hazel extract and aloe vera, allantoin, emollients, disinfectants, hydroxy acids for wrinkle control or anti-aging effects, sunscreens, tanning promoters, skin lighteners, deodorants and anti-perspirants, ceramides for skin benefits and other uses, astringents, moisturizers, nail polish removers, insect repellants, antioxidants, antiseptics, anti-inflammatory agents and the like, provided that the additives are compatible with an binder composition associated therewith, and especially the binder compositions of the present invention (i.e., they do not cause a substantial loss of strength in the wet state of the pre-moistened wipes, prior to dilution in water, while permitting dispersibility in water).
Useful materials for skin care and other benefits are listed in McCutcheon's 1999, Vol. 2: Functional Materials, MC Publishing Company, Glen Rock, N.J. Many useful botanicals for skin care are provided by Active Organics, Lewisville, Tex.
Odor Control Additives
Suitable odor control additives for use in the wetting composition and pre-moistened wipes of the present invention include, but are not limited to, zinc salts; talc powder; encapsulated perfumes (including microcapsules, macrocapsules, and perfume encapsulated in liposomes, vessicles, or microemulsions); chelants, such as ethylenediamine tetra-acetic acid; zeolites; activated silica, activated carbon granules or fibers; activated silica particulates; polycarboxylic acids, such as citric acid; cyclodextrins and cyclodextrin derivatives; chitosan or chitin and derivatives thereof; oxidizing agents; antimicrobial agents, including silver-loaded zeolites (e.g., those of BF Technologies, located in Beverly, Mass., sold under the trademark HEALTHSHIELD™; triclosan; kieselguhr; and mixtures thereof. In addition to controlling odor from the body or body wastes, odor control strategies can also be employed to mask or control any odor of the treated substrate. Desirably, the wetting composition contains less than about 5 weight percent of odor control additives based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 2 weight percent of odor control additives. Even more desirably, the wetting composition contains from about 0.03 weight percent to about 1 weight percent of odor control additives.
In one embodiment of the present invention, the wetting composition and/or pre-moistened wipes comprise derivatized cyclodextrins, such as hydroxypropyl beta-cyclodextrin in solution, which remain on the skin after wiping and provide an odor-absorbing layer. In other embodiments, the odor source is removed or neutralized by application of an odor-control additive, exemplified by the action of a chelant that binds metal groups necessary for the function of many proteases and other enzymes that commonly produce an odor. Chelating the metal group interferes with the enzyme's action and decreases the risk of malodor in the product.
Principles for the application of chitosan or chitin derivatives to nonwoven webs and cellulosic fibers are described by S. Lee et al. in “Antimicrobial and Blood Repellent Finishes for Cotton and Nonwoven Fabrics Based on Chitosan and Fluoropolymers,” Textile Research Journal, 69(2); 104-112, Feb. 1999.
While elevated salt concentrations may reduce the tack of the binder, other means of tack reduction are often desirable. Thus, detackifying agents may be used in the wetting composition to reduce the tackiness, if any, of the binder. Suitable detackifiers include any substance known in the art to reduce tack between two adjacent fibrous sheets treated with an adhesive-like polymer or any substance capable of reducing the tacky feel of an adhesive-like polymer on the skin. Detackifiers may be applied as solid particles in dry form, as a suspension or as a slurry of particles. Deposition may be by spray, coating, electrostatic deposition, impingement, filtration (i.e, a pressure differential drives a particle-laden gas phase through the substrate, depositing particles by a filtration mechanism), and the like, and may be applied uniformly on one or more surfaces of the substrate or may be applied in a pattern (e.g., repeating or random patterns) over a portion of the surface or surfaces of the substrate. The detackifier may be present throughout the thickness of the substrate, but may be concentrated at one or both surfaces, and may be substantially only present on one or both surfaces of the substrate.
Specific detackifiers include, but are not limited to, powders, such as talc powder, calcium carbonate, mica; starches, such as corn starch; lycopodium powder; mineral fillers, such as titanium dioxide; silica powder; alumina; metal oxides in general; baking powder; kieselguhr; and the like. Polymers and other additives having low surface energy may also be used, including a wide variety of fluorinated polymers, silicone additives, polyolefins and thermoplastics, waxes, debonding agents known in the paper industry including compounds having alkyl side chains such as those having 16 or more carbons, and the like. Compounds used as release agents for molds and candle making may also be considered, as well as, dry lubricants and fluorinated release agents.
In one embodiment, the detackifier comprises polytetrafluorethylene (PTFE), such as PTFE telomer (KRYTOX® DF) compound, used in the PTFE release agent dry lubricant MS-122DF, marketed by Miller-Stephenson (Danbury, Conn.) as a spray product. For example, PTFE particles may be applied by spray to one side of the substrate prior to winding of the pre-moistened wipes. In one embodiment, a detackifying agent is applied to only one surface of the substrate prior to winding into a roll.
The wetting composition desirably contains less than about 25 weight percent of detackifying agents based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 10 weight percent of detackifying agents, more specifically about 5% or less. Even more specifically, the wetting composition contains from about 0.05 weight percent to about 2 weight percent of detackifying agents.
In addition to acting as a detackifying agent, starch compounds may also improve the strength properties of the pre-moistened wipes. For example, it has been found that ungelled starch particles, such as hydrophilic tapioca starch, when present at a level of about 1% or higher by weight relative to the weight of the wetting composition improves wet strength. Starch may be applied by adding the starch to a suspension of laponite to improve the dispersion of the starch within the wetting composition.
The wetting composition of the present invention may be further modified by the addition of solid particulates or microparticulates. Suitable particulates include, but are not limited to, mica, silica, alumina, calcium carbonate, kaolin, talc, and zeolites. The particulates may be treated with stearic acid or other additives to enhance the attraction or bridging of the particulates to the binder system, if desired. Also, two-component microparticulate systems, commonly used as retention aids in the papermaking industry, may also be used. Such two-component microparticulate systems generally comprise a colloidal particle phase, such as silica particles, and a water-soluble cationic polymer for bridging the particles to the fibers of the web to be formed. The presence of particulates in the wetting composition can serve one or more useful functions, such as (1) increasing the opacity of the pre-moistened wipes; (2) modifying the rheology or reducing the tackiness of the pre-moistened wipe; (3) improving the tactile properties of the wipe; or (4) delivering desired agents to the skin via a particulate carrier, such as a porous carrier or a microcapsule. Desirably, the wetting composition contains less than about 25 weight percent of particulate based on the total weight of the wetting composition. More specifically, the wetting composition may contain from about 0.05 weight percent to about 10 weight percent of microparticulate. Even more specifically, the wetting composition may contain from about 0.1 weight percent to about 5 weight percent of microparticulate.
Microcapsules and Other Delivery Vehicles
Microcapsules and other delivery vehicles may also be used in the wetting composition of the present invention to provide skin-care agents; medications; comfort promoting agents, such as eucalyptus; perfumes; skin care agents; odor control additives; vitamins; powders; and other additives to the skin of the user. Specifically, the wetting composition may contain up to about 25 weight percent of microcapsules or other delivery vehicles based on the total weight of the wetting composition. More specifically, the wetting composition may contain from about 0.05 weight percent to about 10 weight percent of microcapsules or other delivery vehicles. Even more specifically, the wetting composition may contain from about 0.2 weight percent to about 5.0 weight percent of microcapsules or other delivery vehicles.
Microcapsules and other delivery vehicles are well known in the art. For example, POLY-PORE® E200 (Chemdal Corp., Arlington Heights, Ill.), is a delivery agent comprising soft, hollow spheres that can contain an additive at over 10 times the weight of the delivery vehicle. Known additives reported to have been used with POLY-PORE® E200 include, but are not limited to, benzoyl peroxide, salicylic aid, retinol, retinyl palmitate, octyl methoxycinnamate, tocopherol, silicone compounds (DC 435), and mineral oil. Another useful delivery vehicle is a sponge-like material marketed as POLY-PORE® L200, which is reported to have been used with silicone (DC 435) and mineral oil. Other known delivery systems include cyclodextrins and their derivatives, liposomes, polymeric sponges, and spray-dried starch.
Additives present in microcapsules are isolated from the environment and the other agents in the wetting composition until the wipe is applied to the skin, whereupon the microcapsules break and deliver their load to the skin or other surfaces.
Preservatives and Anti-Microbial Agents
The wetting composition of the present invention may also contain preservatives and/or anti-microbial agents. Several preservatives and/or anti-microbial agents, such as Mackstat H 66 (available from McIntyre Group, Chicago, Ill.), have been found to give excellent results in preventing bacteria and mold growth. Other suitable preservatives and anti-microbial agents include, but are not limited to DMDM hydantoin (e.g., Glydant Plus™, Lonza, Inc., Fair Lawn, N.J.), iodopropynyl butylcarbamate, Kathon (Rohm and Hass, Philadelphia, Pa.), methylparaben, propylparaben, 2-bromo-2-nitropropane-1,3-diol, benzoic acid, and the like. Desirably, the wetting composition contains less than about 2 weight percent on an active basis of preservatives and/or anti-microbial agents based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 1 weight percent of preservatives and/or anti-microbial agents. Even more desirably, the wetting composition contains from about 0.01 weight percent to about 0.5 weight percent of preservatives and/or anti-microbial agents.
Wetting Agents and Cleaning Agents
A variety of wetting agents and/or cleaning agents may be used in the wetting composition of the present invention. Suitable wetting agents and/or cleaning agents include, but are not limited to, detergents and nonionic, amphoteric, and anionic surfactants, especially amino acid-based surfactants. Amino acid-based surfactant systems, such as those derived from amino acids L-glutamic acid and other natural fatty acids, offer pH compatibility to human skin and good cleansing power, while being relatively safe and providing improved tactile and moisturization properties compared to other anionic surfactants. One function of the surfactant is to improve wetting of the dry substrate with the wetting composition. Another function of the surfactant can be to disperse bathroom soils when the pre-moistened wipe contacts a soiled area and to enhance their absorption into the substrate. The surfactant can further assist in make-up removal, general personal cleansing, hard surface cleansing, odor control, and the like.
One commercial example of an amino-acid based surfactant is acylglutamate, marketed under the Amisoft name by Ajinomoto Corp., Tokyo, Japan. Desirably, the wetting composition contains less than about 3 weight percent of wetting agents and/or cleaning agents based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 2 weight percent of wetting agents and/or cleaning agents. Even more desirably, the wetting composition contains from about 0.1 weight percent to about 0.5 weight percent of wetting agents and/or cleaning agents.
Although amino-acid based surfactants are particularly useful in the wetting compositions of the present invention, a wide variety of surfactants may be used in the present invention. Suitable non-ionic surfactants include, but are not limited to, the condensation products of ethylene oxide with a hydrophobic (oleophilic) polyoxyalkylene base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds desirably has a molecular weight sufficiently high so as to render it water-insoluble. The addition of polyoxyethylene moieties to this hydrophobic portion increases the water-solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product. Examples of compounds of this type include commercially-available Pluronic surfactants (BASF Wyandotte Corp.), especially those in which the polyoxypropylene ether has a molecular weight of about 1500-3000 and the polyoxyethylene content is about 35-55% of the molecule by weight, i.e. Pluronic L-62.
Other useful nonionic surfactants include, but are not limited to, the condensation products of C8-C22 alkyl alcohols with 2-50 moles of ethylene oxide per mole of alcohol. Examples of compounds of this type include the condensation products of C11-C15 secondary alkyl alcohols with 3-50 moles of ethylene oxide per mole of alcohol, which are commercially-available as the Poly-Tergent SLF series from Olin Chemicals or the TERGITOL™ series from Union Carbide, i.e. TERGITOL™ 25-L-7, which is formed by condensing about 7 moles of ethylene oxide with a C12-C15 alkanol.
Other nonionic surfactants, which may be employed in the wetting composition of the present invention, include the ethylene oxide esters of C6-C12 alkyl phenols such as (nonylphenoxy)polyoxyethylene ether. Particularly useful are the esters prepared by condensing about 8-12 moles of ethylene oxide with nonylphenol, i.e. the IGEPAL® CO series (GAF Corp.).
Further non-ionic surface active agents include, but are not limited to, alkyl polyglycosides (APG), derived as a condensation product of dextrose (D-glucose) and a straight or branched chain alcohol. The glycoside portion of the surfactant provides a hydrophile having high hydroxyl density, which enhances water solubility. Additionally, the inherent stability of the acetal linkage of the glycoside provides chemical stability in alkaline systems. Furthermore, unlike some non-ionic surface active agents, alkyl polyglycosides have no cloud point, allowing one to formulate without a hydrotrope, and these are very mild, as well as readily biodegradable non-ionic surfactants. This class of surfactants is available from Horizon Chemical under the trade names of APG-300, APG-350, APG-500, and APG-500.
Silicones are another class of wetting agents available in pure form, or as microemulsions, macroemulsions, and the like. One exemplary non-ionic surfactant group is the silicone-glycol copolymers. These surfactants are prepared by adding poly(lower)alkylenoxy chains to the free hydroxyl groups of dimethylpolysiloxanols and are available from the Dow Coming Corp as Dow Coming 190 and 193 surfactants (CTFA name: dimethicone copolyol). These surfactants function, with or without any volatile silicones used as solvents, to control foaming produced by the other surfactants, and also impart a shine to metallic, ceramic, and glass surfaces.
Anionic surfactants may also be used in the wetting compositions of the present invention. Anionic surfactants are useful due to their high detergency include anionic detergent salts having alkyl substituents of 8 to 22 carbon atoms such as the water-soluble higher fatty acid alkali metal soaps, e.g., sodium myristate and sodium palmitate. A preferred class of anionic surfactants encompasses the water-soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal detergent salts containing a hydrophobic higher alkyl moiety (typically containing from about 8 to 22 carbon atoms) such as salts of higher alkyl mono or polynuclear aryl sulfonates having from about 1 to 16 carbon atoms in the alkyl group, with examples available as the Bio-Soft series, i.e. Bio-Soft D-40 (Stepan Chemical Co.).
Other useful classes of anionic surfactants include, but are not limited to, the alkali metal salts of alkyl naphthalene sulfonic acids (methyl naphthalene sodium sulfonate, Petro AA, Petrochemical Corporation); sulfated higher fatty acid monoglycerides such as the sodium salt of the sulfated monoglyceride of cocoa oil fatty acids and the potassium salt of the sulfated monoglyceride of tallow fatty acids; alkali metal salts of sulfated fatty alcohols containing from about 10 to 18 carbon atoms (e.g., sodium lauryl sulfate and sodium stearyl sulfate); sodium C14-C16-alphaolefin sulfonates such as the Bio-Terge series (Stepan Chemical Co.); alkali metal salts of sulfated ethyleneoxy fatty alcohols (the sodium or ammonium sulfates of the condensation products of about 3 moles of ethylene oxide with a C12-C15 n-alkanol, i.e., the Neodol ethoxysulfates, Shell Chemical Co.); alkali metal salts of higher fatty esters of low molecular weight alkylol sulfonic acids, e.g. fatty acid esters of the sodium salt of isothionic acid, the fatty ethanolamide sulfates; the fatty acid amides of amino alkyl sulfonic acids, e.g. lauric acid amide of taurine; as well as numerous other anionic organic surface active agents such as sodium xylene sulfonate, sodium naphthalene sulfonate, sodium toulene sulfonate and mixtures thereof.
A further useful class of anionic surfactants includes the 8-(4-n-alkyl-2-cyclohexenyl)-octanoic acids, wherein the cyclohexenyl ring is substituted with an additional carboxylic acid group. These compounds or their potassium salts, are commercially-available from Westvaco Corporation as Diacid 1550 or H-240. In general, these anionic surface active agents can be employed in the form of their alkali metal salts, ammonium or alkaline earth metal salts.
Macroemulsions and Microemulsion of Silicone Particles
The wetting composition may further comprise an aqueous microemulsion of silicone particles. For example, U.S. Pat. No. 6,037,407, “Process for the Preparation of Aqueous Emulsions of Silicone Oils and/or Gums and/or Resins” issued Mar. 14, 2000, discloses organopolysiloxanes in an aqueous microemulsion. Desirably, the wetting composition contains less than about 5 weight percent of a microemulsion of silicone particles based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.02 weight percent to about 3 weight percent of a microemulsion of silicone particles. Even more desirably, the wetting composition contains from about 0.02 weight percent to about 0.5 weight percent of a microemulsion of silicone particles.
Silicone emulsions in general may be applied to the pre-moistened wipe by any known coating method. For example, the pre-moistened wipe may be moistened with an aqueous composition comprising a water-dispersible or water-miscible, silicone-based component that is compatible with the activating compound in the wetting composition. Further, the wipe can comprise a nonwoven web of fibers having a water-dispersible binder, wherein the web is moistened with a lotion comprising a silicone based sulfosuccinate. The silicone-based sulfosuccinate provides gentle and effective cleansing without a high level of surfactant. Additionally, the silicone-based sulfosuccinate provides a solubilization function, which prevents precipitation of oil-soluble components, such as fragrance components, vitamin extracts, plant extracts, and essential oils.
In one embodiment of the present invention, the wetting composition comprises a silicone copolyol sulfosuccinate, such as disodium dimethicone copolyol sulfosuccinate and diammonium dimethicone copolyolsulfosuccinate. Desirably, the wetting composition comprises less than about 2 percent by weight of the silicone-based sulfosuccinate, and more desirably from about 0.05 percent to about 0.30 percent by weight of the silicone-based sulfosuccinate.
In another example of a product comprising a silicone emulsions, Dow Coming 9506 powder may also be present in the wetting composition. Dow Coming 9506 powder is believed to comprise a dimethicone/vinyldimethicone cross-polymer and is a spherical powder, which is said to be useful in controlling skin oils (see “New Chemical Perspectives,” Soap and Cosmetics, Vol. 76, No. 3, Mar. 2000, p. 12). Thus, a water-dispersible wipe, which delivers a powder effective in controlling skin oil, is also within the scope of the present invention. Principles for preparing silicone emulsions are disclosed in WO 97/10100, published Mar. 20, 1997.
The wetting composition of the present invention may also contain one or more emollients. Suitable emollients include, but are not limited to, PEG 75 lanolin, methyl gluceth 20 benzoate, C12-C15 alkyl benzoate, ethoxylated cetyl stearyl alcohol, products marketed as Lambent wax WS-L, Lambent WD-F, Cetiol HE (Henkel Corp.), Glucam P20 (Amerchol), Polyox WSR N-10 (Union Carbide), Polyox WSR N-3000 (Union Carbide), Luviquat (BASF), Finsolv SLB 101 (Finetex Corp.), mink oil, allantoin, stearyl alcohol, Estol 1517 (Unichema), and Finsolv SLB 201 (Finetex Corp.).
An emollient can also be applied to a surface of the article prior to or after wetting with the wetting composition. Such an emollient may be insoluble in the wetting composition and can be immobile except when exposed to a force. For example, a petrolatum-based emollient can be applied to one surface in a pattern, after which the other surface is wetted to saturate the wipe. Such a product could provide a cleaning surface and an opposing skin treatment surface.
The emollient composition in such products and other products of the present invention can comprise a plastic or fluid emollient such as one or more liquid hydrocarbons (e.g., petrolatum), mineral oil and the like, vegetable and animal fats (e.g., lanolin, phospholipids and their derivatives) and/or a silicone materials such as one or more alkyl substituted polysiloxane polymers, including the polysiloxane emollients disclosed in U.S. Pat. No. 5,891,126, issued Apr. 6, 1999 to Osborn, III et al. Optionally, a hydrophilic surfactant may be combined with a plastic emollient to improve wettability of the coated surface. In some embodiments of the present invention, it is contemplated that liquid hydrocarbon emollients and/or alkyl substituted polysiloxane polymers may be blended or combined with one or more fatty acid ester emollients derived from fatty acids or fatty alcohols.
In an embodiment of the present invention, the emollient material is in the form of an emollient blend. Desirably, the emollient blend comprises a combination of one or more liquid hydrocarbons (e.g., petrolatum), mineral oil and the like, vegetable and animal fats (e.g., lanolin, phospholipids and their derivatives), with a silicone material such as one or more alkyl substituted polysiloxane polymers. More desirably, the emollient blend comprises a combination of liquid hydrocarbons (e.g., petrolatum) with dimethicone or with dimethicone and other alkyl substituted polysiloxane polymers. In some embodiments of the present invention, it is contemplated that blends of liquid hydrocarbon emollients and/or alkyl substituted polysiloxane polymers may be blended with one or more fatty acid ester emollients derived from fatty acids or fatty alcohols. PEG-7 glyceryl cocoate, available as Standamul HE (Henkel Corp., Hoboken, N.J.), can also be considered.
Water-soluble, self-emulsifying emollient oils, which are useful in the present wetting compositions, include the polyoxyalkoxylated lanolins and the polyoxyalkoxylated fatty alcohols, as disclosed in U.S. Pat. No. 4,690,821, issued Sep. 1, 1987 to Smith et al. The polyoxyalkoxy chains desirably will comprise mixed propylenoxy and ethyleneoxy units. The lanolin derivatives will typically comprise about 20-70 such lower-alkoxy units while the C12-C20-fatty alcohols will be derivatized with about 8-15 lower-alkyl units. One such useful lanolin derivative is Lanexol AWS (PPG-12-PEG-50, Croda, Inc., New York, N.Y.). A useful poly(15-20) C2-C3-alkoxylate is PPG-5-Ceteth-20, known as Procetyl AWS (Croda, Inc.).
According to one embodiment of the present invention, the emollient material reduces undesirable tactile attributes, if any, of the wetting composition. For example, emollient materials, including dimethicone, can reduce the level of tackiness that may be caused by the binder or other components in the wetting composition, thus serving as a detackifier.
Desirably, the wetting composition contains less than about 25 weight percent of emollients based on the total weight of the wetting composition. More specifically, the wetting composition may comprise less than about 5 weight percent emollient, and most specifically less than about 2% emollient. More desirably, the wetting composition may contain from about 0.01 weight percent to about 8 weight percent of emollients. Even more desirably, the wetting composition may contain from about 0.2 weight percent to about 2 weight percent of emollients.
In one embodiment, the wetting composition and/or pre-moistened wipes of the present invention comprise an oil-in-water emulsion comprising an oil phase containing at least one emollient oil and at least one emollient wax stabilizer dispersed in an aqueous phase comprising at least one polyhydric alcohol emollient and at least one organic water-soluble detergent, as disclosed in U.S. Pat. No. 4,559,157, issued Dec. 17, 1985 to Smith et al., the entirety of which is herein incorporated by reference.
Surface Feel Modifiers
Surface feel modifiers are used to improve the tactile sensation (e.g., lubricity) of the skin during use of the product. Suitable surface feel modifiers include, but are not limited to, commercial debonders; and softeners, such as the softeners used in the art of tissue making including quaternary ammonium compounds with fatty acid side groups, silicones, waxes, and the like. Exemplary quaternary ammonium compounds with utility as softeners are disclosed in U.S. Pat. No. 3,554,862, issued to Hervey et al. on Jan. 12, 1971; U.S. Pat. No. 4,144,122, issued to Emanuelsson et al., Mar. 13, 1979, U.S. Pat. No. 5,573,637, issued to Ampulski et al. Nov. 12, 1996; and U.S. Pat. No. 4,476,323, issued to Hellsten et al., Oct. 9, 1984, the entirety of all of which is herein incorporated by reference. Desirably, the wetting composition contains less than about 2 weight percent of surface feel modifiers based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 1 weight percent of surface feel modifiers. Even more desirably, the wetting composition contains from about 0.01 weight percent to about 0.05 weight percent of surface feel modifiers.
A variety of fragrances may be used in the wetting composition of the present invention. Desirably, the wetting composition contains less than about 2 weight percent of fragrances based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 1 weight percent of fragrances. Even more desirably, the wetting composition contains from about 0.01 weight percent to about 0.05 weight percent of fragrances.
Further, a variety of fragrance solubilizers may be used in the wetting composition of the present invention. Suitable fragrance solubilizers include, but are not limited to, polysorbate 20, propylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, Ameroxol OE-2 (Amerchol Corp.), Brij 78 and Brij 98 (ICI Surfactants), Arlasolve 200 (ICI Surfactants), Calfax 16L-35 (Pilot Chemical Co.), Capmul POE-S (Abitec Corp.), Finsolv SUBSTANTIAL (Finetex), and the like. Desirably, the wetting composition contains less than about 2 weight percent of fragrance solubilizers based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 1 weight percent of fragrance solubilizers. Even more desirably, the wetting composition contains from about 0.01 weight percent to about 0.05 weight percent of fragrance solubilizers.
Suitable opacifiers include, but are not limited to, titanium dioxide or other minerals or pigments, and synthetic opacifiers such as REACTOPAQUE® particles (available from Sequa Chemicals, Inc., Chester, S.C.). Desirably, the wetting composition contains less than about 2 weight percent of opacifiers based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 1 weight percent of opacifiers. Even more desirably, the wetting composition contains from about 0.01 weight percent to about 0.05 weight percent of opacifiers.
pH Control Agents
Suitable pH control agents for use in the wetting composition of the present invention include, but are not limited to, malic acid, citric acid, hydrochloric acid, acetic acid, sodium hydroxide, potassium hydroxide, and the like. An appropriate pH range minimizes the amount of skin irritation resulting from the wetting composition on the skin. Desirably, the pH range of the wetting composition is from about 3.5 to about 6.5. More desirably, the pH range of the wetting composition is from about 4 to about 6. Desirably, the wetting composition contains less than about 2 weight percent of a pH adjuster based on the total weight of the wetting composition. More desirably, the wetting composition contains from about 0.01 weight percent to about 1 weight percent of a pH adjuster. Even more desirably, the wetting composition contains from about 0.01 weight percent to about 0.05 weight percent of a pH adjuster.
Although a variety of wetting compositions, formed from one or more of the above-described components, may be used with the wet wipes of the present invention, in one embodiment, the wetting composition contains the following components, given in weight percent of the wetting composition, as shown in Table 2 below:
Wetting Composition Components
Wetting Composition Component:
about 86 to about 98
about 5 to about 20
Up to about 2
Up to about 2
Up to about 1
Up to about 1
Up to about 0.3
Up to about 0.5
Up to about 0.2
In another embodiment of the present invention, the wetting composition comprises the following components, given in weight percent of the wetting composition, as shown in Table 3 below:
Wetting Composition Components
Class of Wetting
about 86 to
about 5 to
Up to about 2
Up to about 2
Up to about 1
Skin Feel agent)
Up to about 1
Up to about 0.3
Up to about 0.5
St. Paul, MN)
Malic Acid to
Up to about 0.2
pH 5 (Haarman
In another embodiment of the present invention, the wetting composition comprises the following components, given in weight percent of the wetting composition, as shown in Table 4 below:
An Exemplary Wetting Composition
Class of Wetting
Malic Acid to
It should be noted that the above-described wetting compositions of the present invention may be used with any one of the above-described binder compositions of the present invention. Further, the above-described wetting compositions of the present invention may be used with any other binder composition, including conventional binder compositions, or with any known fibrous or absorbent substrate, whether dispersible or not.
Unless otherwise specified, tensile testing is performed according to the following protocol. Testing of dry product should be conducted under Tappi conditions (50% relative humidity, 73° F.) with a procedure similar to ASTM-1117-80, section 7. Tensile tests are performed with a constant crosshead speed tensile tester such as the Thwing Albert 1256-100 tensile tester with an RSA-210-kg load cell. Specimens are cut to 3-inch widths and 6 inch lengths, and mounted between jaws with a 4-inch gauge length. The crosshead speed is 12 inches per minute. Peak load (for tensile strength) and elongation at peak load (for stretch) are measured. For cross direction (CD) tensile tests, the sample is cut in the cross direction. For machine direction (MD) tensile tests, the sample is cut in the cross direction.
Tensile tests in the dry state are reported for webs taken prior to application of the wetting composition. The machine direction dry tensile strength is abbreviated as “MDDT,” and the cross direction dry tensile strength as “CDDT.” The results can be reported as kg/3-in or converted to units of g/in or g/2.54 cm.
Based on the dry weight of the specimen cut to the appropriate size, an excess amount of wetting solution (4% saline solution with no other additives, unless otherwise specified) is applied to reach a solution add-on of 250-400%. The wetted specimens are then immediately passed through an Atlas Lab Wringer (Atlas Electric Devices Company, Chicago, Ill. No. 10404 LW-1, no load) to uniformly distribute the solution in the sample and gently remove the excess solution to achieve a final solution add-on of 200%. Several iterations or passes may be needed to reach the add-on target depending on the sample. The completed, pre-moistened samples are then bagged in plastic to prevent dry-out before testing.
Cross direction wet tensile tests (CDWT) or machine direction wet tensile strength (MDWT) are performed as described above using the pre-moistened sample as is, after the sample has equilibrated by sitting overnight in a sealed plastic bag.
For tests related to strength loss in a pre-moistened web occurring after exposure to a new solution, a container having dimensions of 200 mm by 120 mm and deep enough to hold 1000 ml is filled with 700 ml of the selected soak solution. No more than 108 square inches of sample are soaked in the 700 ml of soaking solution, depending on specimen size. The pre-moistened specimens, that have equilibrated overnight, are immersed in the soak solution and then allowed to soak undisturbed for a specified time period (typically 1 hour). At the completion of the soak period, samples are carefully retrieved from the soak solution, allowed to drain, and then tested immediately as described above (i.e., the sample is immediately mounted in the tensile tester and tested, without being passed through the wringer). In cases with highly dispersible materials, the samples often cannot be retrieved from the soaking solution without falling apart. The soaked tensile values for such samples are recorded as zero for the corresponding solution.
For the deionized soaked cross-direction wet tensile test, S-CDWT, the sample is immersed in deionized water for 1 hour and then tested. For the hard-water soaked cross-direction wet tensile test, S-CDWT-M (M indicating divalent metal ions), the sample is immersed in water containing 200 ppm of Ca++/Mg++ in a 2:1 ratio prepared from calcium chloride and magnesium chloride, soaked for one hour and then tested. For the medium hard water soaked cross-direction wet tensile test, MS-CDWT-M, the sample is immersed in water containing 50 ppm of Ca++/Mg++ in a 2:1 ratio, soaked for one hour and then tested. Testing done with other time increments or soaking solutions should be so indicated to prevent confusion with the S-CDWT or S-CDWT-M tests.
The amount of wetting composition added to the nonwoven fabric, relative to the weight of the dry nonwoven fabric in the present invention, is desirably about 180 percent to about 240 weight percent.
Desirably, the wet wipes of the present invention possess an in-use wet tensile strength (CDWT) of at least 100 g/in, and a tensile strength of less than about 30 g/in after being soaked in water having a concentration of Ca2 + and/or Mg2 + ions of about 50 ppm for about one hour (MS-CDWT-M). More desirably, the wet wipes possess an in-use wet tensile strength of at least 300 g/in (CDWT), and a tensile strength of less than about 30 g/in after being soaked in water having a concentration of Ca2 + and/or Mg2+ ions of about 50 ppm for about one hour (MS-CDWT-M). In a further embodiment, the wet wipes desirably possess an in-use wet tensile strength of at least 200 g/in (CDWT), and a tensile strength of less than about 20 g/in after being soaked in water having a concentration of Ca2+ and/or Mg2 + ions of about 200 ppm for about one hour (S-CDWT-M). Even more desirably, the wet wipes possess an in-use wet tensile strength of at least 300 g/in, and a tensile strength of less than about 20 g/in after being soaked in water having a concentration of Ca2 + and/or Mg2 + ions of about 200 ppm for about one hour (S-CDWT-M).
Products with high basis weights or wet strengths than flushable wet wipes may have relatively higher wet tensile strength. For example, products such as pre-moistened towels or hard-surface cleaning wipes may have basis weights above 70 gsm, such as from 80 gsm to 150 gsm. Such products can have CDWT values of 500 g/in or greater, with S-CDWT values of about 150 g/in or less, more specifically about 100 g/in or less, and most specifically about 50 g/in or less, with similar ranges possible for S-CDWT-M.
Prior efforts to measure dispersibility of webs, whether dry or premoistened, have commonly relied on systems in which the web was exposed to shear while in water, such as measuring the time for a web to break up while being agitated by a mechanical mixer. The constant exposure to shear offers an unrealistic and overly optimistic test for products designed to be flushed in a toilet, where the level of shear is weak and extremely brief. Once the product has passed through the neck of the toilet and entered a septic tank, shear rates may be negligible. Further, the product may not be fully wetted with water from the toilet bowl when it is flushed, or rather, there may not have been adequate time for the wetting composition of the product to have been replaced with the water of the toilet bowl when the momentary shear of flushing is applied. Thus, previous measurements of dispersibility could suggest that a product is dispersible when, in fact, it may be poorly suited for septic system.
For a realistic appraisal of dispersibility, it is believed that a relatively static measure is needed to better simulate the low shear that real products will experience once they have become fully wetted with water from the toilet. Thus, a test method for dispersibility has been developed which does not rely on shear and which provides an improved means of assessing suitability of a product for a septic system. In this method, the tensile strength of a product is measured in its original, wetted form (the CDWT measurement described above) and after the product has been soaked in a second solution for one hour (either the S-CDWT or S-CDWT-M test). The second solution can be either deionized water for determination of the “Deionized Dispersibility” value or hard water (according to the S-CDWT-M test) for determination of the “Hard Water Dispersibility” value. In either case, the Dispersibility is defined as (1 minus the ratio of the cross-direction wet tensile strength in the second solution divided by the original cross-direction wet tensile strength) * 100%. Thus, if a pre-moistened wipe loses 75% of its CD wet tensile strength after soaking in hard water for one hour, the Hard Water Dispersibility is (1-0.25)*100%=75%. The articles of the present invention can have a Deionized Dispersibility of 80% or greater, more specifically 90% or greater, specifically still 95% or greater, and can have a Deionized Dispersibility of about 100%. The articles of the present invention can have a Hard Water Dispersibility of 70% or greater, more specifically 80% or greater, specifically still about 90% or greater, and can have a Deionized Dispersibility of about 100%.
Method of Making Wet Wipes
The pre-moistened wipes of the present invention can be made in several ways. In one embodiment, the polymer composition is applied to a fibrous substrate as part of an aqueous solution or suspension, wherein subsequent drying is needed to remove the water and promote binding of the fibers. In particular, during drying, the binder migrates to the crossover points of the fibers and becomes activated as a binder in those regions, thus providing acceptable strength to the substrate. For example, the following steps can be applied:
1. Providing an absorbent substrate that is not highly bonded (e.g., an unbonded airlaid, a tissue web, a carded web, fluff pulp, etc.).
2. Applying an polymer composition to the substrate, typically in the form of a liquid, suspension, or foam.
3. Drying the substrate to promote bonding of the substrate. The substrate may be dried such that the peak substrate temperature does not exceed 160° C., or 140° C., or 120° C., 110° C., or 100° C. In one embodiment, the substrate temperature does not exceed 80° C. or 60° C.
4. Applying a wetting composition to the substrate.
5. Placing the wetted substrate in roll form or in a stack and packaging the product.
Application of the polymer composition to the substrate can be by means of spray; by foam application; by immersion in a bath; by curtain coating; by coating and metering with a wire-wound rod; by passage of the substrate through a flooded nip; by contact with a pre-metered wetted roll coated with the binder solution; by pressing the substrate against a deformable carrier containing the polymer composition, such as a sponge or felt, to effect transfer into the substrate; by printing such as gravure, inkjet, or flexographic printing; and any other means known in the art.
In the use of foams to apply a polymer binder, the mixture is frothed, typically with a foaming agent, and spread uniformly on the substrate, after which vacuum is applied to pull the froth through the substrate. Any known foam application method can be used, including that of U.S. Pat. No. 4,018,647, “Process for the Impregnation of a Wet Fiber Web with a Heat Sensitized Foamed Latex Binder,” issued Apr. 19, 1977 to Wietsma, the entirety of which is herein incorporated by reference. Wietsma discloses a method wherein a foamed latex is heat-sensitized by the addition of a heat-sensitizer such as functional siloxane compounds including siloxane oxyalkylene block copolymers and organopolysiloxanes. Specific examples of applicable heat-sensitizers and their use thereof for the heat sensitization of latices are described in the U.S. Pat. Nos. 3,255,140; 3,255,141; 3,483,240 and 3,484,394, all of which are incorporated herein by reference. The use of a heat-sensitizer is said to result in a product having a very soft and textile-like hand compared to prior methods of applying foamed latex binders.
The amount of heat-sensitizer to be added is dependent on, inter alia, the type of latex used, the desired coagulation temperature, the machine speed and the temperatures in the drying section of the machine, and will generally be in the range of about 0.05 to about 3% by weight, calculated as dry matter on the dry weight of the latex; but also larger or smaller amounts may be used. The heat sensitizer can be added in such an amount that the latex will coagulate far below the boiling point of water, for instance at a temperature in the range of 35° C. to 95° C., or from about 35° C. to 65° C.
Without wishing to be bound by theory, it is believed that a drying step after application of the binder solution and before application of the wetting composition enhances bonding of a fibrous substrate by driving the binder to fiber crossover points as moisture is driven off, thus promoting efficient use of the binder. However, in an alternative method, the drying step listed above is skipped, and the polymer composition is applied to the substrate followed by application of the wetting composition without significant intermediate drying. In one version of this method, the polymer composition selectively adheres to the fibers, permitting excess water to be removed in an optional pressing step without a significant loss of the binder from the substrate. In another version, no significant water removal occurs prior to application of the wetting composition. In yet another alternative method, the polymer composition and the wetting composition are applied simultaneously, optionally with subsequent addition of water-compatible organic solvent.
The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the present invention and/or the scope of the appended claims.
As used herein, the “thickness” of a web is measured with a 3-in acrylic plastic disk connected to the spindle of a Mitutoyo Digimatic Indicator (Mitutoyo Corporation, 31-19, Shiba 5-chome, Minato-ku, Tokyo 108, Japan) and which delivers a net load of 0.05 psi to the sample being measured. The Mitutoyo Digimatic Indicator is zeroed when the disk rests on a flat surface. When a sample having a size at least as great as the acrylic disk is placed under the disk, a thickness reading can be obtained from the digital readout of the indicator. Water-dispersible substrates of the present invention can have any suitable thickness, such as from about 0.1 mm to 5 mm. For wet wipes, thicknesses can be in the range of 0.2 mm to about 1 mm, more specifically from about 0.3 mm to about 0.7 mm. Thickness can be controlled, for example, by the application of compaction rolls during or after web formation, by pressing after binder or wetting composition has been applied, or by controlling the tension of winding when forming a roll good.
The use of the platen method to measure thickness gives an average thickness at the macroscopic level. Local thickness may vary, especially if the product has been embossed or has otherwise been given a three-dimensional texture.
The nine binder solutions shown below were applied via a #20 wire-wound rod to 10 identical water-dispersible, wet-laid webs composed of BFE rayon fibers (1.5 d×25 mm). The fabric samples were dried in a forced-air oven at 500° C. The add-on level was between 150 and 200 wt % based on the total weight of the fabric. The nonwoven sheets were cut to provide 1 inch×3 inch strips from each sheet. The strips were tested for CDWT and SCDWT according to the following procedure.
The 1″×3″ strips from the 10 nonwoven sheets were soaked in the wipe solutions #1-#10 for 12 hours. The samples were removed from the solutions and tested for tensile strength in the cross direction using the procedure outlined above.
The 1″×3″ strips from the 10 nonwoven sheets were soaked in a solution of 200 ppm Ca2+ for 1 hour. The samples were removed from the solutions and tested for tensile strength in the cross direction using the procedure outlined above.
The results are shown in Table 4 below.
Technical Performance of Kao's Binder
(Mwt = 400,000)
(Mwt = 400,000)
(Mwt = 400,000),
(Tg = ˜ −15 C)
(Mwt = 400,000),
(Tg = ˜ −7 C)
(Mwt = 400,000),
(Tg = ˜ −7 C)
(Mwt = 400,000),
(Tg = ˜ −4 C)
(Mwt = 400,000),
(Tg = ˜ −4 C)
It should be understood, of course, that the foregoing relates only to certain disclosed embodiments of the present invention and that numerous modifications or alterations may be made therein without departing from the spirit and scope of the invention as set forth in the appended claims.
|Patente citada||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US2265913||20 Oct 1937||9 Dic 1941||Lilienfeld Patents Inc||Hydroxy alkyl-alkyl ethers of cellulose|
|US2831852||27 May 1954||22 Abr 1958||Dow Chemical Co||Water-soluble thermoplastic cellulose ethers|
|US3097991||10 Jun 1957||16 Jul 1963||Union Carbide Corp||Synthetic fibrous products|
|US3099067||30 Nov 1959||30 Jul 1963||Union Carbide Corp||Plastic fibers|
|US3340327||13 Mar 1961||5 Sep 1967||Desoto Inc||Fumaric acid-polyoxyalkylene glycoldicyclopentadiene polyesters curable with vinyl monomer and mixtures thereof|
|US3388082||1 Nov 1965||11 Jun 1968||Dow Chemical Co||Novel hydroxypropyl methyl cellulose ethers, a process for preparing the same, and compositions utilizing such ethers|
|US3407164||26 Ago 1965||22 Oct 1968||Standard Brands Chem Ind Inc||Polymeric dispersion, articles impregnated therewith and methods therefor|
|US3461193||4 Ene 1967||12 Ago 1969||Du Pont||Novel procedure for starting the flash-extrusion of expandable resin compositions|
|US3480016||3 Sep 1968||25 Nov 1969||Celanese Corp||Sanitary products|
|US3485705||8 Nov 1966||23 Dic 1969||Johnson & Johnson||Nonwoven fabric and method of manufacturing the same|
|US3515325||5 Mar 1968||2 Jun 1970||Johnson & Johnson||Apparatus for fibrillating a transversely oriented plastic material|
|US3521638||10 Feb 1969||28 Jul 1970||Du Pont||Fabrics having water soluble discrete areas and methods of making|
|US3554788||9 Oct 1968||12 Ene 1971||Johnson & Johnson||Water dispersible nonwoven fabric|
|US3561447||13 Mar 1969||9 Feb 1971||Kendall & Co||Flushable sanitary napkin|
|US3564677||6 Nov 1967||23 Feb 1971||Johnson & Johnson||Method and apparatus of treating material to change its configuration|
|US3577586||20 Dic 1967||4 May 1971||Johnson & Johnson||Apparatus for continuously transversely stretching orientable sheet material|
|US3616797||6 Feb 1970||2 Nov 1971||Kimberly Clark Co||Flushable wrapper for absorbent pads|
|US3639199||15 Dic 1969||1 Feb 1972||Cons Paper Bahamas Ltd||Reinforced laminate product|
|US3654064||30 Oct 1969||4 Abr 1972||David H E Laumann||Water-disintegratable sheet material|
|US3663348||16 May 1968||16 May 1972||Johnson & Johnson||A lofty and soft nonwoven, through bonded fabric|
|US3665923||5 Feb 1970||30 May 1972||Kimberly Clark Co||Flushable sanitary napkin|
|US3670069||15 Sep 1969||13 Jun 1972||Itt||Process for forming hydroxyethyl cellulose fibers having high water absorption and high water retention properties|
|US3670731||20 May 1966||20 Jun 1972||Johnson & Johnson||Absorbent product containing a hydrocolloidal composition|
|US3683919||15 Ene 1970||15 Ago 1972||Myron B Ells||Flushable sanitary napkin|
|US3692725||28 Oct 1970||19 Sep 1972||Kimberly Clark Co||Stabilized binder for water-flushable non-woven webs|
|US3709876||10 Abr 1972||9 Ene 1973||Dow Chemical Co||Water soluble hydroxyethyl methyl cellulose ether thickener for latex paint|
|US3712847||28 Sep 1970||23 Ene 1973||O Rasmussen||Laminated lamellar laminate|
|US3719540||4 May 1970||6 Mar 1973||Hercules Inc||Preparation of transversely fibrillated film|
|US3753826||17 Mar 1971||21 Ago 1973||Johnson & Johnson||Methods of making nonwoven textile fabrics|
|US3804092||15 Ene 1973||16 Abr 1974||Johnson & Johnson||Water dispersible nonwoven fabric|
|US3808165||21 Ago 1972||30 Abr 1974||Kimberly Clark Co||Stabilized polyvinyl alcohol binder solution for water-flushable non-woven webs|
|US3838695||17 Sep 1973||1 Oct 1974||Personal Products Co||Flushable sanitary napkin|
|US3859125||10 Oct 1972||7 Ene 1975||Gilbreth Co||Soluble coated paper|
|US3865918||22 Mar 1972||11 Feb 1975||Itt||Wet spinning cellulosic products|
|US3867549||28 Jun 1972||18 Feb 1975||Colgate Palmolive Co||Stable starch compositions|
|US3869310||1 Dic 1972||4 Mar 1975||Kuraray Co||Flexible sheet materials|
|US3881210||24 Mar 1972||6 May 1975||Scott Paper Co||Flushable, pre-moistened, sanitary wiper and method of manufacturing same|
|US3881487||30 Jul 1973||6 May 1975||Kimberly Clark Co||Flushable disposable diaper structure|
|US3882869||31 Ene 1972||13 May 1975||Kimberly Clark Co||Water-dispersible plastic tampon insertion tubes and the like|
|US3911917||21 Nov 1974||14 Oct 1975||Kimberly Clark Co||Injector device for tampons or the like made from odor-free thermoformed heat-degraded polyvinyl alcohol|
|US3913579||15 Oct 1974||21 Oct 1975||Personal Products Co||Flushable sanitary napkin|
|US3923592||31 Jul 1974||2 Dic 1975||Riegel Textile Corp||Process for manufacturing a flushable fibrous sheet material for use in sanitary products|
|US3946158||25 Abr 1975||23 Mar 1976||Leclercq Marc A||Video-telephone system initially signifies caller to called subscriber|
|US3950578||9 Jun 1971||13 Abr 1976||Richard S. Keoseian||Water-disintegratable sheet material|
|US3951900||26 Dic 1973||20 Abr 1976||National Gypsum Company||Fire-retardant adhesive|
|US3952745||19 Nov 1974||27 Abr 1976||The Procter & Gamble Company||Disposable diaper having readily flushable absorbent media and improved pad intergrity in use|
|US3978257||6 Ago 1973||31 Ago 1976||Kimberly-Clark Corporation||Internally adhesively bonded fibrous web|
|US4002171||17 Mar 1975||11 Ene 1977||Personal Products Company||Water-dispersible ionic polyurethane binder for nonwoven fabrics|
|US4009139 *||22 May 1975||22 Feb 1977||Basf Aktiengesellschaft||Opacifying agents|
|US4009313||30 Ago 1972||22 Feb 1977||Minnesota Mining And Manufacturing Company||Enzymatically dispersible non-woven webs|
|US4011871||17 Mar 1975||15 Mar 1977||Personal Products Company||Water-dispersible barrier films for body fluid retention|
|US4035540||29 Dic 1975||12 Jul 1977||Johnson & Johnson||Non-woven fabrics bonded with pH sensitive film-forming silane crosslinked acrylate interpolymers|
|US4041203||4 Oct 1976||9 Ago 1977||Kimberly-Clark Corporation||Nonwoven thermoplastic fabric|
|US4082886||15 Ago 1977||4 Abr 1978||Johnson & Johnson||Liquid absorbent fibrous material and method of making the same|
|US4084033||7 Jun 1976||11 Abr 1978||Johnson & Johnson||Bonded nonwoven fabrics|
|US4100324||19 Jul 1976||11 Jul 1978||Kimberly-Clark Corporation||Nonwoven fabric and method of producing same|
|US4112167||7 Ene 1977||5 Sep 1978||The Procter & Gamble Company||Skin cleansing product having low density wiping zone treated with a lipophilic cleansing emollient|
|US4117187||29 Dic 1976||26 Sep 1978||American Can Company||Premoistened flushable wiper|
|US4136798||16 Ago 1976||30 Ene 1979||Oberstein N||Flushable bedpan bag|
|US4141713||20 Abr 1977||27 Feb 1979||Saint Gobain Industries||Apparatus for extracting a glass ribbon from the egress of a flotation furnace|
|US4164595||5 Sep 1978||14 Ago 1979||American Can Company||Premoistened flushable wiper|
|US4186233||27 Mar 1978||29 Ene 1980||The Dow Chemical Company||Disposable composite insensitive to surface moisture but disintegratable in aqueous liquid|
|US4201216||9 Feb 1979||6 May 1980||Ethicon, Inc.||Absorbable coating composition for sutures|
|US4220244||9 Jun 1978||2 Sep 1980||Sabra Elmore||Fresh face pad|
|US4226753||15 May 1978||7 Oct 1980||Rohm And Haas Company||Novel methacrylic polymers having condensation-crosslinkable functionality|
|US4251416||21 Nov 1979||17 Feb 1981||United States Gypsum Company||Carpet backing adhesive|
|US4301203||29 Feb 1980||17 Nov 1981||Pnc Company||Manufacturing a thermoplastic non-woven web comprising coherently interconnected filaments|
|US4306998||8 Jul 1980||22 Dic 1981||Bayer Aktiengesellschaft||Process for the preparation of stable aqueous dispersions of oligourethanes or polyurethanes and their use as coating compounds for flexible or rigid substrates|
|US4309469||13 Abr 1979||5 Ene 1982||Scott Paper Company||Flushable binder system for pre-moistened wipers wherein an adhesive for the fibers of the wipers interacts with ions contained in the lotion with which the wipers are impregnated|
|US4325861||3 Abr 1980||20 Abr 1982||Union Carbide Corporation||Rapidly dissolved water-soluble polymer composition|
|US4332319||25 Jun 1980||1 Jun 1982||Hurwood David L||Hygienic comfort product|
|US4333464||11 Abr 1980||8 Jun 1982||Zenmi Co., Ltd.||Sanitary napkin|
|US4343133||26 Jun 1980||10 Ago 1982||Air Products And Chemicals, Inc.||Polyvinyl acetate latex impregnated towelette|
|US4343134||26 Jun 1980||10 Ago 1982||Air Products And Chemicals, Inc.||Flushable towelette|
|US4344804||21 Nov 1979||17 Ago 1982||Stamicarbon B.V.||Process and apparatus for the manufacture of fiber-reinforced hydraulically bound articles such as cementitious articles|
|US4362781||21 Sep 1981||7 Dic 1982||Scott Paper Company||Flushable premoistened wiper|
|US4377544||20 Jul 1981||22 Mar 1983||Rasmussen O B||Manufacture of a textile-like reticular product from thermoplastic film|
|US4377645||26 Oct 1981||22 Mar 1983||W. R. Grace & Co.||Dimensionally-stable polyurethane sponge and sponge-forming prepolymer|
|US4385019||19 Ene 1981||24 May 1983||Mpd Technology Corporation||Production of a polymeric active composition|
|US4425126||14 Oct 1980||10 Ene 1984||Johnson & Johnson Baby Products Company||Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers|
|US4440105||17 Ene 1983||3 Abr 1984||Consolidated Papers, Inc.||Paper coating apparatus having a replaceable orifice plate|
|US4494278||9 Mar 1982||22 Ene 1985||Karl Kristian Kobs Kroyer||Apparatus for the production of a fibrous web|
|US4496619||16 Nov 1982||29 Ene 1985||Toray Industries, Inc.||Fabric composed of bundles of superfine filaments|
|US4511687||28 May 1982||16 Abr 1985||Daicel Chemical Industries, Ltd.||Polycaprolactone composition|
|US4512279||10 Jun 1983||23 Abr 1985||Consolidated Papers, Inc.||Paper coating apparatus|
|US4528360||17 Sep 1984||9 Jul 1985||Dai-Ichi Kogyo Seiyaku Co., Ltd.||Water-soluble film or sheet|
|US4537807||16 Abr 1984||27 Ago 1985||The Borden Company, Limited||Binder for pre-moistened paper products|
|US4543128||23 Ago 1983||24 Sep 1985||Sandoz Ltd.||Fillers dyed with polycationic dyestuffs useful for coloring paper and non-woven fabrics|
|US4575891||9 Nov 1984||18 Mar 1986||Mark Valente||Toilet seat disinfectant wipe|
|US4585835||24 Dic 1984||29 Abr 1986||Unitika Ltd.||Polymer compositions|
|US4588400||16 Dic 1982||13 May 1986||Johnson & Johnson Products, Inc.||Liquid loaded pad for medical applications|
|US4592850||4 Mar 1985||3 Jun 1986||The Goodyear Tire & Rubber Company||Injection water viscosifier for enhanced oil recovery|
|US4594389||15 Oct 1984||10 Jun 1986||The Goodyear Tire & Rubber Company||Blends of higher α- olefin polymers and 1,2-epoxide polymers|
|US4600404||16 Nov 1984||15 Jul 1986||Kimberly-Clark Corporation||Heat sealable water dispersible adhesive|
|US4617235||23 May 1984||14 Oct 1986||Unitika Ltd.||Antistatic synthetic fibers|
|US4627950||24 Abr 1985||9 Dic 1986||Kanebo, Ltd.||Method of producing abrasive fibers|
|US4711725||7 May 1986||8 Dic 1987||Rohm And Haas Co.||Method of stabilizing aqueous systems|
|US4725489||4 Dic 1986||16 Feb 1988||Airwick Industries, Inc.||Disposable semi-moist wipes|
|US4732797||27 Feb 1987||22 Mar 1988||James River Corporation||Wet wiper natural acid preservation system|
|US4737405||31 Oct 1986||12 Abr 1988||James River Corporation||Binder catalyst for an antimicrobially active, non-woven web|
|US4738992||17 Jun 1986||19 Abr 1988||Minnesota Mining And Manufacturing Company||Hydrophilic polyurethane/polyurea sponge|
|US4740398||30 Sep 1985||26 Abr 1988||James River Corporation||Binder catalyst for an antimicrobially active, non-woven web|
|US4744830||26 Nov 1986||17 May 1988||Agency Of Industrial Science & Technology||Fibrous binder and a method for the preparation thereof|
|US4753844||5 Nov 1987||28 Jun 1988||Airwick Industries Inc.||Disposable semi-moist wipes|
|US4755421||7 Ago 1987||5 Jul 1988||James River Corporation Of Virginia||Hydroentangled disintegratable fabric|
|US4772492||30 Dic 1987||20 Sep 1988||James River Corporation||Binder catalyst for an antimicrobially active, non-woven web|
|US4772501||3 Dic 1987||20 Sep 1988||James River Corporation||Wet wiper natural acid preservation system|
|US4781974||9 Mar 1987||1 Nov 1988||James River Corporation||Antimicrobially active wet wiper|
|US4792326||30 Mar 1987||20 Dic 1988||Kimberly-Clark Corporation||Rapidly disintegrating paper tubes|
|US4795668||31 Jul 1987||3 Ene 1989||Minnesota Mining And Manufacturing Company||Bicomponent fibers and webs made therefrom|
|US4814131||2 Jul 1987||21 Mar 1989||Atlas Sheldon M||Process for producing a shaped article, such as fiber composed of a hydrophobic polymer and a hydrophilic polymer|
|US4837078||17 Dic 1987||6 Jun 1989||Hercules Incorporated||Wet/dry wipes|
|US4902559||11 May 1988||20 Feb 1990||Firma Carl Freudenberg||Absorbent body of nonwoven material and a method for the production thereof|
|US4930942||11 Oct 1988||5 Jun 1990||E. R. Squibb & Sons, Inc.||Method of disposal of articles by flushing|
|US4966808||23 Ene 1990||30 Oct 1990||Chisso Corporation||Micro-fibers-generating conjugate fibers and woven or non-woven fabric thereof|
|US4998984||15 Nov 1989||12 Mar 1991||Mcclendon Evelyn||Premoistened prepackaged disposable disinfectant wiper|
|US5026363||27 Dic 1989||25 Jun 1991||Rmed International, Inc.||Flushable diaper device and method|
|US5033172||1 Jun 1989||23 Jul 1991||Hercules Incorporated||Rewettable polyolefin fiber and corresponding nonwovens|
|US5045387||28 Jul 1989||3 Sep 1991||Hercules Incorporated||Rewettable polyolefin fiber and corresponding nonwovens|
|US5049440||28 Jul 1989||17 Sep 1991||The James River Corporation||Wet wiper natural acid and salt preservative composition|
|US5053482||11 May 1990||1 Oct 1991||E. I. Du Pont De Nemours And Company||Novel polyesters and their use in compostable products such as disposable diapers|
|US5057361||17 Nov 1989||15 Oct 1991||Kimberly-Clark Corporation||Wettable polymeric fabrics|
|US5096640||27 Ene 1989||17 Mar 1992||Imperial Chemical Industries Plc||Method of producing porous hollow fibrous tubes|
|US5097004||25 Ene 1991||17 Mar 1992||E. I. Du Pont De Nemours And Company||Novel polyesters and their use in compostable products such as disposable diapers|
|US5097005||25 Ene 1991||17 Mar 1992||E. I. Du Pont De Nemours And Company||Novel copolyesters and their use in compostable products such as disposable diapers|
|US5102601||19 Dic 1988||7 Abr 1992||Farris Richard J||Process for fabricating novel compostes based on reinforcement with microfibrillar networks of rigid-rod polymers|
|US5104367||20 Nov 1990||14 Abr 1992||Filter Materials Limited||Pinned rollers and process for manufacturing fibrillated film|
|US5120598||2 Ago 1991||9 Jun 1992||Air Products And Chemicals, Inc.||Fibrous material for oil spill clean-up|
|US5145727||26 Nov 1990||8 Sep 1992||Kimberly-Clark Corporation||Multilayer nonwoven composite structure|
|US5149335||23 Feb 1990||22 Sep 1992||Kimberly-Clark Corporation||Absorbent structure|
|US5149576||26 Nov 1990||22 Sep 1992||Kimberly-Clark Corporation||Multilayer nonwoven laminiferous structure|
|US5171402||6 Jun 1991||15 Dic 1992||E. I. Du Pont De Nemours And Company||Dispersible aramid pulp|
|US5178646||4 Jun 1992||12 Ene 1993||Minnesota Mining And Manufacturing Company||Coatable thermally curable binder presursor solutions modified with a reactive diluent, abrasive articles incorporating same, and methods of making said abrasive articles|
|US5178812||28 Nov 1990||12 Ene 1993||E. I. Du Pont De Nemours And Company||Method of making composites having improved surface properties|
|US5181966||30 Jun 1992||26 Ene 1993||Honeycutt Travis W||Hot water soluble packaging materials|
|US5181967||19 May 1992||26 Ene 1993||Isolyser Company, Inc.||Method of disposal of hot water soluble utensils|
|US5182162||24 Oct 1990||26 Ene 1993||Amoco Corporation||Self-bonded nonwoven web and net-like web composites|
|US5196470||1 Mar 1991||23 Mar 1993||H. B. Fuller Licensing & Financing Inc.||Water soluble alcohol based nonwoven binder for water swellable, soluble or sensitive fibers|
|US5204104||7 Oct 1991||20 Abr 1993||Pre Pak Products||Physical therapy massage stick and process|
|US5205968||28 Dic 1990||27 Abr 1993||The Dow Chemical Company||Process for making a microporous membrane from a blend containing a poly(etheretherketone)-type polymer, an amorphous polymer, and a solvent|
|US5206064||18 Abr 1991||27 Abr 1993||Minnesota Mining And Manufacturing Company||Curable resins with solid supported antifoaming agents|
|US5207662||17 Ago 1992||4 May 1993||Annett James||Flushable or disposable diaper pad with reusable wrap|
|US5207837||12 May 1992||4 May 1993||Honeycutt Travis W||Method of disposal of hot water soluble garments and like fabrics|
|US5208098||23 Oct 1990||4 May 1993||Amoco Corporation||Self-bonded nonwoven web and porous film composites|
|US5217495||13 Nov 1990||8 Jun 1993||United States Surgical Corporation||Synthetic semiabsorbable composite yarn|
|US5217798||7 May 1991||8 Jun 1993||National Starch And Chemical Investment Holding Corporation||Water sensitive hot melt adhesives for nonwoven applications|
|US5219646||13 Feb 1992||15 Jun 1993||E. I. Du Pont De Nemours And Company||Polyester blends and their use in compostable products such as disposable diapers|
|US5227101||21 Dic 1990||13 Jul 1993||The Dow Chemical Company||Process of making microporous membranes from poly(etheretherketone)-type polymers and low melting point crystallizable polymers|
|US5246647||19 Ago 1991||21 Sep 1993||The Dow Chemical Company||Process of making microporous hollow fiber or film membrane of poly(phenylene sulfide) (PPS)|
|US5252332||24 Jul 1992||12 Oct 1993||Air Products And Chemicals, Inc.||Pre-moistened flushable towlette impregnated with polyvinyl alcohol containing binders|
|US5256417||31 Ene 1992||26 Oct 1993||Air Products And Chemicals, Inc.||Water dispersible towelette impregnated with non-aqueous lotion formulations|
|US5257982||21 Oct 1992||2 Nov 1993||Hercules Incorporated||Fluid absorbing article utilizing a flow control cover sheet|
|US5264269||23 Ago 1990||23 Nov 1993||Kao Corporation||Water-disintegratable cleaning article in laminated sheet form|
|US5264491||26 Ago 1992||23 Nov 1993||Edison Polymer Innovation Corporation||Compatibilization of polymer blends|
|US5270358||25 Jun 1992||14 Dic 1993||Minnesota Mining And Manufacturing Company||Composite of a disperesed gel in an adhesive matrix|
|US5275699||7 Oct 1992||4 Ene 1994||University Of Washington||Compositions and methods for filling dried cellulosic fibers with an inorganic filler|
|US5281306||2 Abr 1992||25 Ene 1994||Kao Corporation||Water-disintegrable cleaning sheet|
|US5286538||3 Ago 1992||15 Feb 1994||Leonard Pearlstein||Disposable container for moist paper towels the same|
|US5292581||15 Dic 1992||8 Mar 1994||The Dexter Corporation||Wet wipe|
|US5295985||6 Nov 1992||22 Mar 1994||E. I. Du Pont De Nemours And Company||Polyesters and their use in compostable products such as disposable diapers|
|US5300192||17 Ago 1992||5 Abr 1994||Weyerhaeuser Company||Wet laid fiber sheet manufacturing with reactivatable binders for binding particles to fibers|
|US5304420||20 Ago 1992||19 Abr 1994||Kuraray Co., Ltd.||Vinyl alcohol unit-containing polymer fibers having high moisture absorption and high water absorption|
|US5330827||3 Ago 1992||19 Jul 1994||Danaklon A/S||Reinforcing fibres and a method of producing the same|
|US5330832||22 Mar 1993||19 Jul 1994||Amoco Corporation||Pressure-sensitive adhesives of polyvinyl methyl ether|
|US5334176||23 Jul 1991||2 Ago 1994||The Procter & Gamble Company||Absorbent core for use in catamenial products|
|US5346541||18 Nov 1992||13 Sep 1994||Net/Tech International, Inc.||Water dispersible formulations and materials and methods for influencing their water dispersibility|
|US5356963||16 Jul 1993||18 Oct 1994||National Starch And Chemical Investment Holding Corporation||Hydrophilic hot melt adhesives|
|US5362565||12 May 1993||8 Nov 1994||Nippon Paper Industries Co., Ltd.||Production method of microcapsules|
|US5366804||31 Mar 1993||22 Nov 1994||Basf Corporation||Composite fiber and microfibers made therefrom|
|US5369155||1 Jul 1993||29 Nov 1994||Minnesota Mining And Manufacturing Company||Composite of a dispersed gel in an adhesive matrix and method for preparing same|
|US5393602||19 Abr 1991||28 Feb 1995||Bioelastics Research Ltd.||Superabsorbent materials and uses thereof|
|US5400982||9 May 1994||28 Mar 1995||Fort Howard Corporation||Dispenser for multiple rolls of sheet material|
|US5405342||29 Jun 1994||11 Abr 1995||Kimberly-Clark Corporation||Disposable absorbent article with flushable insert|
|US5407442||23 Nov 1993||18 Abr 1995||Karapasha; Nancy||Carbon-containing odor controlling compositions|
|US5409747||19 Nov 1993||25 Abr 1995||Leonard Pearlstein||Disposable container for moist paper towels and a method of making the same|
|US5415643||7 Dic 1992||16 May 1995||Kimberly-Clark Corporation||Flushable absorbent composites|
|US5415813||22 Nov 1993||16 May 1995||Colgate-Palmolive Company||Liquid hard surface cleaning composition with grease release agent|
|US5437908||12 May 1994||1 Ago 1995||Jujo Kimberly K.K.||Bathroom tissue and process for producing the same|
|US5439521||6 May 1994||8 Ago 1995||Rao; Muralidhara S.||Dispenser for storing and dispensing moistened toilet tissue|
|US5442016||20 Abr 1994||15 Ago 1995||American Cyanamid Company||Coating for tissue drag reduction|
|US5443084||7 May 1991||22 Ago 1995||Saleur; Remy||Paper moistener device and moist toilet paper dispenser|
|US5449127||14 Dic 1993||12 Sep 1995||Davis; Robert T.||Dispenser for rolls of sheet material|
|US5449551||3 Jun 1993||12 Sep 1995||Kawano Paper Co., Ltd.||Highly water absorbent fibrous web and a process for producing the same|
|US5458591||14 Feb 1995||17 Oct 1995||Kimberly-Clark Corporation||Disposable absorbent article with flushable insert|
|US5464170||16 Feb 1994||7 Nov 1995||Scott Paper Company||Toilet tissue roll adaptor|
|US5466410||11 May 1994||14 Nov 1995||Basf Corporation||Process of making multiple mono-component fiber|
|US5466518||17 Ago 1993||14 Nov 1995||Kimberly-Clark Corporation||Binder compositions and web materials formed thereby|
|US5470640||24 Nov 1993||28 Nov 1995||Hercules Incorporated||High loft and high strength nonwoven fabric|
|US5470941||23 Dic 1993||28 Nov 1995||Sunkyong Industries||Thermoplastic biodegradable resins and a process of preparation thereof|
|US5473789||18 Oct 1993||12 Dic 1995||Oster; Alan L.||Disposable toilet seat cleaning pad|
|US5476457||14 Feb 1995||19 Dic 1995||Kimberly-Clark Corporation||Disposable absorbent article with flushable insert|
|US5476909||7 Feb 1994||19 Dic 1995||Sam Yang Co., Ltd.||Biodegradable copolymer for medical application|
|US5480060||8 Ago 1994||2 Ene 1996||Scott Paper Company||Space saving system for coreless rolled wipers|
|US5486307||15 Nov 1994||23 Ene 1996||Colgate-Palmolive Co.||Liquid cleaning compositions with grease release agent|
|US5494250||29 Jul 1994||27 Feb 1996||Chen; Wen-Yen||Cleaning tissue holder|
|US5495997||4 Oct 1994||5 Mar 1996||James River Paper Company, Inc.||Support apparatus for coreless toilet tissue roll|
|US5500068||5 Jun 1995||19 Mar 1996||International Paper Company||Absorbent, flushable, bio-degradable, medically-safe nonwoven fabric with PVA binding fibers, and process for making the same|
|US5514380||30 Jun 1994||7 May 1996||Sam Yang Co., Ltd.||Biodegradable hydrogel copolymer as drug delivery matrix|
|US5516432||21 Nov 1994||14 May 1996||Rohm And Haas Company||Method for prevention of scale formation in aqueous systems|
|US5519085||7 Ago 1995||21 May 1996||E. I. Du Pont De Nemours And Company||Aqueous dispersions containing ABC triblock polymer dispersants|
|US5522841||29 Dic 1994||4 Jun 1996||United States Surgical Corporation||Absorbable block copolymers and surgical articles fabricated therefrom|
|US5530074||7 Jun 1995||25 Jun 1996||American Cyanamid Company||Coating for tissue drag reduction|
|US5532300||12 Ago 1994||2 Jul 1996||National Starch And Chemical Investment Holding Corporation||Water-borne, water redispersible, laminating adhesives for nonwoven applications|
|US5532306||31 Ago 1994||2 Jul 1996||National Starch And Chemical Investment Holding Corporation||Water-sensitive rubber-based hot melt adhesives|
|US5534178||12 Dic 1994||9 Jul 1996||Ecolab Inc.||Perforated, stable, water soluble film container for detersive compositions|
|US5534229||20 Dic 1994||9 Jul 1996||Nomura & Shibatani||Volatilization suppressing agent|
|US5542566||23 Nov 1994||6 Ago 1996||Kimberly-Clark Corporation||Reusable dispenser and a plurality of disposable child mitt wipes contained therein|
|US5545472||22 Feb 1995||13 Ago 1996||National Starch And Chemical Investment Holding Corporation||Water-borne, water redispersible, laminating adhesives for nonwoven applications|
|US5569230||30 May 1995||29 Oct 1996||The Procter & Gamble Company||Individually packaged sanitary napkin having cleaning wipe packaged therewith|
|US5576364||22 May 1995||19 Nov 1996||Kimberly-Clark Corporation||Hydrodisintegratable binder compositions|
|US5578344||22 Nov 1995||26 Nov 1996||The Procter & Gable Company||Process for producing a liquid impermeable and flushable web|
|US5589545||18 Jul 1994||31 Dic 1996||Union Carbide Chemicals & Plastics Technology Corporation||Lubricious polymer blends comprising polyethylene oxide, polyethylene and a polylactone|
|US5612404||21 Dic 1995||18 Mar 1997||Ppg Industries, Inc.||Aqueous, anionic, amino acrylate coating compositions|
|US5613959||14 Feb 1995||25 Mar 1997||Kimberly-Clark Corporation||Disposable absorbent article with flushable insert|
|US5616201||8 May 1995||1 Abr 1997||Kimberly-Clark Corporation||Process for making a child's mitt wipe|
|US5619911||31 Oct 1995||15 Abr 1997||Mecatherm||Oven for continous baking of bread, Viennese bread, pastry products and the like|
|US5620788||16 Jul 1993||15 Abr 1997||Kimberly-Clark Corporation||Wettable polymeric fabrics with durable surfactant treatment|
|US5629081||31 Mar 1995||13 May 1997||Kimberly-Clark Tissue Corporation||Premoistened, flushable, disposable and biodegradable wet wipes|
|US5647862||10 Ago 1995||15 Jul 1997||The Procter & Gamble Company||Absorbent article with means for directional fluid distribution|
|US5647863||21 Sep 1995||15 Jul 1997||The Procter & Gamble Company||Absorbent article with clean appearance and capacity signal means|
|US5648083||10 Feb 1995||15 Jul 1997||The Procter & Gamble Company||Personal care compositions and wipe products containing the compositions|
|US5649336||23 Nov 1994||22 Jul 1997||Kimberly-Clark Worldwide, Inc.||Child's mitt wipe|
|US5667635||18 Sep 1996||16 Sep 1997||Kimberly-Clark Worldwide, Inc.||Flushable premoistened personal wipe|
|US5670110||21 Dic 1995||23 Sep 1997||The Procter & Gamble Company||Method for making three-dimensional macroscopically-expanded webs having improved functional surfaces|
|US5684075||21 Feb 1995||4 Nov 1997||Phillips Petroleum Company||Compositions comprising an acrylamide-containing polymer and process therewith|
|US5693698||30 May 1995||2 Dic 1997||Phillips Petroleum Company||Compositions comprising an acrylamide-containing polymer and process therewith|
|US5695551||9 Dic 1996||9 Dic 1997||Dow Corning Corporation||Water repellent composition|
|US5698322||2 Dic 1996||16 Dic 1997||Kimberly-Clark Worldwide, Inc.||Multicomponent fiber|
|US5714157||29 Ago 1994||3 Feb 1998||E. I. Du Pont De Nemours And Company||Water-dispersible granular agricultural compositions made by heat extrusion|
|US5725789||31 Mar 1995||10 Mar 1998||Minnesota Mining And Manufacturing Company||Aqueous oil and water repellent compositions|
|US5725821||19 Jun 1995||10 Mar 1998||Courtaulds Fibres (Holdings) Limited||Process for the manufacture of lyocell fibre|
|US5756112||14 Ene 1997||26 May 1998||The Procter & Gamble Company||Carrier substrate treated with high internal water phase inverse emulsion made with an organopolysiloxane-polyoxyalkylene emulsifier|
|US5763044||22 Nov 1995||9 Jun 1998||The Procter & Gamble Company||Fluid pervious, dispersible, and flushable webs having improved functional surface|
|US5763332||5 Dic 1996||9 Jun 1998||The Procter & Gamble Company||Cleaning articles comprising a polarphobic region and a high internal phase inverse emulsion|
|US5765717||9 Abr 1997||16 Jun 1998||Gottselig; John C.||Wet hygienic towel dispenser|
|US5766758||19 Mar 1997||16 Jun 1998||Kuraray Co., Ltd.||Fiber of ethylene-vinyl alcohol copolymer and process for production thereof|
|US5800417||12 Dic 1995||1 Sep 1998||Goerg-Wood; Kristin Ann||Absorbent composition comprising hydrogel-forming polymeric material and fiber bundles|
|US5804203||20 Jun 1996||8 Sep 1998||Cosmederm Technologies||Topical product formulations containing strontium for reducing skin irritation|
|US5807364||4 Abr 1995||15 Sep 1998||Weyerhaeuser Company||Binder treated fibrous webs and products|
|US5837627||13 Ene 1997||17 Nov 1998||Weyerhaeuser Company||Fibrous web having improved strength and method of making the same|
|US5846230||1 Jul 1997||8 Dic 1998||The Procter & Gamble Co.||Absorbent article with means for directional fluid distribution|
|US5849805||13 Oct 1995||15 Dic 1998||The Procter & Gamble Company||Process for making foams useful as absorbent members for catamenial pads|
|US5858342||5 Ene 1996||12 Ene 1999||The Procter & Gamble Company||Cleansing compositions|
|US5866675||29 Ago 1997||2 Feb 1999||H. B. Fuller Licensing & Financing, Inc.||Nonwoven web comprising water soluble polyamides and articles constructed therefrom|
|US5869596||14 May 1998||9 Feb 1999||H. B. Fuller Licensing & Financing, Inc.||Fibers comprising water soluble polyamides and articles constructed therefrom|
|US5871763||24 Abr 1997||16 Feb 1999||Fort James Corporation||Substrate treated with lotion|
|US5899893||20 Oct 1997||4 May 1999||The Procter & Gamble Company||Absorbent articles containing foams useful for absorbing blood and blood-based liquids|
|US5905046||11 Oct 1996||18 May 1999||Uni-Charm Corporation||Biodegradable and hydrolyzable sheet|
|US5916678||16 Oct 1996||29 Jun 1999||Kimberly-Clark Worldwide, Inc.||Water-degradable multicomponent fibers and nonwovens|
|US5935384||21 Jul 1997||10 Ago 1999||Kawano Paper Co. Ltd||Water-disintegrable paper having moisture retaining property and process for producing the same|
|US5935880||31 Mar 1997||10 Ago 1999||Wang; Kenneth Y.||Dispersible nonwoven fabric and method of making same|
|US5952077||3 Ene 1996||14 Sep 1999||Imperial Chemical Industries Plc||Surfactant compositions|
|US5958555||24 Jun 1997||28 Sep 1999||Uni-Charm Corporation||Disposable wiper sheet|
|US5968286||3 Oct 1997||19 Oct 1999||Helene Curtis, Inc.||Heat-mediated conditioning from shampoo and conditioner hair care compositions containing silicone|
|US5969052||31 Dic 1996||19 Oct 1999||Kimberly Clark Worldwide, Inc.||Temperature sensitive polymers and water-dispersible products containing the polymers|
|US5971138||5 Mar 1998||26 Oct 1999||Soughan; John J.||Toiletries dispensing package|
|US5972805||7 Abr 1998||26 Oct 1999||Kimberly-Clark Worldwide, Inc.||Ion sensitive polymeric materials|
|US5980673||4 Mar 1998||9 Nov 1999||Uni-Charm Corporation||Wiping sheet and method for producing the same|
|US5986004||17 Mar 1997||16 Nov 1999||Kimberly-Clark Worldwide, Inc.||Ion sensitive polymeric materials|
|US6005045||24 Feb 1998||21 Dic 1999||Ppg Industries Ohio, Inc.||Waterborne, ambient temperature curable film-forming compositions|
|US6007585||15 Dic 1998||28 Dic 1999||Avlon Industries, Inc.||Hair brightening system|
|US6010972||24 Mar 1997||4 Ene 2000||Kimberly-Clark Worldwide, Inc.||Oil-resistant disposable absorbent product|
|US6017832||19 Dic 1997||25 Ene 2000||Kimberly-Clark Worldwide, Inc.||Method and composition for treating substrates for wettability|
|US6028016||22 Jul 1997||22 Feb 2000||Kimberly-Clark Worldwide, Inc.||Nonwoven Fabric Substrates Having a Durable Treatment|
|US6031045||12 Ago 1997||29 Feb 2000||H. B. Fuller Licensing & Financing, Inc.||Water-based sulfonated polymer compositions|
|US6042769||19 Jun 1995||28 Mar 2000||Acordis Fibres (Holdings ) Limited||Lyocell fibre and a process for its manufacture|
|US6043317||23 May 1997||28 Mar 2000||Kimberly-Clark Worldwide, Inc.||Ion sensitive binder for fibrous materials|
|US6059882||30 Jun 1998||9 May 2000||The Procter & Gamble Company||Apparatus for dispensing tissue|
|US6059928||18 Sep 1995||9 May 2000||Fort James Corporation||Prewettable high softness paper product having temporary wet strength|
|US6083854||30 Ago 1996||4 Jul 2000||The Procter & Gamble Company||Wet wipes with low viscosity silicone emulsion systems|
|US6093410||5 Nov 1997||25 Jul 2000||The Procter & Gamble Company||Personal care compositions|
|US6098836||30 Mar 1998||8 Ago 2000||Gottselig; John C.||Wet hygienic towel dispenser|
|US6121170||17 Jun 1999||19 Sep 2000||Kimberly-Clark Worldwide, Inc.||Water-sensitive compositions for improved processability|
|US6123811||14 Dic 1998||26 Sep 2000||Ethicon, Inc.||Method of manufacturing aqueous paper pulp for water soluble packages|
|US6127593||25 Nov 1997||3 Oct 2000||The Procter & Gamble Company||Flushable fibrous structures|
|US6171292||28 Dic 1999||9 Ene 2001||The Procter & Gamble Company||Toilet-disposable absorbent interlabial device|
|US6187141||16 Sep 1998||13 Feb 2001||Uni-Charm Corporation||Water-disintegratable fibrous sheet having layered structure and wiping sheet comprising the same|
|US6190502||21 Jul 1998||20 Feb 2001||Uni-Charm Corporation||Water-disintegratable fibrous sheet|
|US6194517||5 Oct 1999||27 Feb 2001||Kimberly-Clark Worldwide, Inc.||Ion sensitive polymeric materials|
|US6218492||24 Abr 1998||17 Abr 2001||Huels Aktiengesellschaft||Water insoluble bacteriophobic polymers containing carboxyl and sulfonic acid groups|
|US6277768||31 Ago 1999||21 Ago 2001||Kimberly Clark Worldwide||Temperature sensitive polymers and water-dispersible products containing the polymers|
|US6294645||25 Jul 1997||25 Sep 2001||Hercules Incorporated||Dry-strength system|
|US20010053753||10 Ago 1999||20 Dic 2001||Carolyn Engekhart||Stable cleansing compositions containing active agents|
|USRE28957||8 May 1975||7 Sep 1976||Johnson & Johnson||Synthetic resin compositions and methods of utilizing the same|
|BE748453A1||Título no disponible|
|CA631395A||21 Nov 1961||Union Carbide Corp||Fine fibers by extrusion and subsequent dissolution of major component|
|CA2057692A1||16 Dic 1991||11 Oct 1992||Travis W. Honeycutt||Method of disposal of hot water soluble fabric|
|DE2513251C3||26 Mar 1975||7 Sep 1978||Bayer Ag, 5090 Leverkusen||Título no disponible|
|EP0027997B2||21 Oct 1980||12 Abr 1995||Plüss-Staufer AG||Mineral filler, particularly calcium carbonate for paints and paper coatings|
|EP0103902A3||22 Sep 1983||19 Feb 1986||Uno Toru||Combustion of logs by lighting the particularly spaced combustible faces by means of an andiron|
|EP0206489B1||12 May 1986||13 Mar 1991||University Of Southern Mississippi||Calcium-tolerant n-substituted acrylamides as thickeners for aqueous systems|
|EP0225800B1||8 Dic 1986||14 May 1997||Minnesota Mining And Manufacturing Company||Hydrophilic polyurethane/polyurea sponge|
|EP0241127B1||3 Mar 1987||13 Oct 1993||Rohm And Haas Company||Textile materials, methods of manufacture and compositions for use therein|
|EP0315466B1||4 Nov 1988||30 Dic 1992||The Dow Chemical Company||Formation of flexible laminates|
|EP0355254A1||26 Abr 1989||28 Feb 1990||Smrz, Peter, Prof. Dr. med.||Textile impregnated with sea salt for therapeutic uses|
|EP0358313B1||11 Jul 1989||25 Ago 1993||Rohm And Haas Company||Method for producing an article containing a radiation cross-linked polymer and the article produced thereby|
|EP0372388B1||30 Nov 1989||16 Feb 1994||Kao Corporation||Water-disintegrable cleaning sheet|
|EP0408199A1||15 Jun 1990||16 Ene 1991||W.R. Grace & Co.-Conn.||Prevention of ammonia generation in animal areas|
|EP0411752B1||1 Jun 1990||26 Jul 1995||The Dexter Corporation||Method for hydroentangling non-woven fibrous sheets|
|EP0421163B1||12 Sep 1990||30 Nov 1994||Kao Corporation||Water-disintegrable cleaning article in laminated sheet form|
|EP0443627B1||25 Feb 1991||4 Jun 1997||Kimberly-Clark Corporation||Absorbent structure|
|EP0445655B2||28 Feb 1991||8 Nov 2000||E.I. Du Pont De Nemours And Company||Dispersible aramid pulp|
|EP0507878B1||13 Dic 1990||12 Abr 1995||Minnesota Mining And Manufacturing Company||Composite of a dispersed gel in an adhesive matrix and method for preparing same|
|EP0510572B1||21 Abr 1992||11 Jun 1997||Air Products And Chemicals, Inc.||Aqueous polyurethane-vinyl polymer dispersions for coating applications|
|EP0525671B1||24 Jul 1992||15 Feb 1995||Kabushiki Kaisha Toyota Chuo Kenkyusho||Synthetic resin composition and interior material coated with the same|
|EP0531112B1||2 Sep 1992||25 Mar 1998||Jujo Kimberly K.K.||Toilet paper and process for producing the same|
|EP0549988B1||21 Dic 1992||3 Jun 1998||Kimberly-Clark Worldwide, Inc.||Hygienic disposable absorbent article|
|EP0572569B1||26 Feb 1992||7 Dic 1994||H.B. FULLER LICENSING & FINANCING, INC.||Water soluble alcohol based nonwoven binder composition|
|EP0580764B1||6 Mar 1992||2 Ene 1997||Minnesota Mining And Manufacturing Company||Curable resins with solid supported antifoaming agents|
|EP0580811B1||10 Mar 1992||4 Ago 1999||Bioelastics Research, Ltd.||Superabsorbent materials and uses thereof|
|EP0582123B1||20 Jul 1993||6 Dic 1995||Air Products And Chemicals, Inc.||Pre-moistened flushable towelette impregnated with polyvinyl alcohol containing binders|
|EP0597978B1||4 Ago 1992||27 Mar 1996||PEARLSTEIN, Leonard||Disposable container for moist paper towels and a method of making the same|
|EP0613675A1||4 Mar 1994||7 Sep 1994||JOHNSON & JOHNSON CONSUMER PRODUCTS, INC.||Cosmetic applicator useful for cleansing, moisturizing and protecting the skin from diaper rash|
|EP0619074A1||30 Mar 1994||12 Oct 1994||Kimberly-Clark Corporation||Antimicrobially effective aqueous solution and preserved wet wipes using same|
|EP0620256A3||16 Mar 1994||29 Mar 1995||Nippon Paint Co Ltd||Polymer composition for hydrophilic treatment.|
|EP0634466A3||15 Jul 1994||6 Mar 1996||Nat Starch Chem Invest||Hydrophilic hot melt adhesives.|
|EP0637950B1||19 Abr 1993||15 Jul 1998||THE PROCTER & GAMBLE COMPANY||Individually packaged sanitary napkin having cleansing wipe packaged therewith|
|EP0639381A1||21 Jul 1994||22 Feb 1995||Kimberly-Clark Corporation||Binder compositions and web materials formed thereby|
|EP0648871B1||11 Oct 1994||9 Dic 1998||Kuraray Co., Ltd.||Water-soluble heat-press-bonding polyvinyl alcohol type binder fiber, nonwoven fabric containing said fiber, and processes for production of said fiber and said nonwoven fabric|
|EP0654492B1||15 Nov 1994||3 Abr 2002||Mitsui Chemicals, Inc.||Degradable aliphatic polyester formed products|
|EP0671496B1||23 Feb 1995||14 Abr 1999||BBA Nonwovens Simpsonville, Inc.||Nonwoven fabric and process for making same|
|EP0672787B1||17 Mar 1995||26 Jun 2002||Georgia-Pacific Corporation||Prewettable high-softness paper product having temporary wet strength|
|EP0689817A2||29 Jun 1995||3 Ene 1996||Kimberly-Clark Corporation||Absorbent structure including an adhesive|
|EP0693915B1||6 Jul 1992||15 Sep 1999||THE PROCTER & GAMBLE COMPANY||Absorbent core for use in catamenial products|
|EP0699727B1||7 Jun 1995||8 Sep 1999||National Starch and Chemical Investment Holding Corporation||Water-sensitive rubber-based hot melt adhesives|
|EP0706361B1||8 Jun 1994||10 Mar 1999||THE PROCTER & GAMBLE COMPANY||Absorbent article with means for directional fluid distribution|
|EP0726068B1||30 Nov 1987||24 Abr 2002||E.R. SQUIBB & SONS, INC.||Method for disposal of articles by flushing|
|EP0761795B1||22 Ago 1996||31 May 2000||National Starch and Chemical Investment Holding Corporation||Hot melt adhesives based on sulfonated polyesters|
|EP0765649B1||25 Feb 1991||13 Jun 2001||Kimberly-Clark Worldwide, Inc.||Absorbent structure|
|EP0766755B1||19 Jun 1995||15 Dic 1999||Acordis Fibres (Holdings) Limited||Lyocell fibre and a process for its manufacture|
|EP0766756B1||19 Jun 1995||2 Sep 1998||Courtaulds Fibres (Holdings) Limited||Process for the manufacture of lyocell fibre|
|EP0768425B1||18 Sep 1996||24 Nov 2004||Fort James Corporation||Prewettable high softness paper product having temporary wet strength|
|EP0773315B1||5 Nov 1996||10 May 2000||H.B. Fuller Licensing & Financing, Inc.||Nonwoven web comprising water soluble polyamides and articles constructed therefrom|
|EP0779387A3||1 Abr 1992||24 Feb 1999||National Starch and Chemical Investment Holding Corporation||Process for the production of a non woven substrate|
|EP0781538B1||18 Nov 1996||7 Ene 2009||H.B. Fuller Licensing & Financing, Inc.||Non-woven application for water dispersable copolyester|
|EP0793743B1||27 Oct 1995||8 Mar 2000||Kimberly-Clark Worldwide, Inc.||Child's mitt wipe and process for making the same|
|EP0801157B1||18 Mar 1997||29 Ene 2003||Kuraray Co., Ltd.||Fiber of ethylene-vinyl alcohol copolymer and process for production thereof|
|EP0802282A4||1 Nov 1996||5 Nov 1997||Título no disponible|
|EP0802804B1||11 Ene 1996||3 Abr 2002||THE PROCTER & GAMBLE COMPANY||Biodegradable polymer-containing compositions|
|EP0807704B1||7 May 1997||2 Nov 2000||Basf Aktiengesellschaft||Recovery of fibres from bonded nonwovens|
|EP0829503B1||10 Sep 1997||3 Abr 2002||Mitsui Chemicals, Inc.||Degradable polymer and preparation process of the same|
|EP0864418B1||6 Mar 1998||1 Oct 2003||Uni-Charm Corporation||Wiping sheet and method for producing the same|
|EP0873100B1||13 Dic 1996||12 Jul 2000||THE PROCTER & GAMBLE COMPANY||Method for making three-dimensional, macroscopically-expanded webs having improved functional surfaces|
|EP0875233A1||24 Abr 1998||4 Nov 1998||Fort James Corporation||Substrate treated with lotion|
|EP0896089B1||4 Ago 1998||15 Oct 2003||Uni-Charm Corporation||Water-disintegratable fibrous sheet|
|EP0904933B1||22 Sep 1998||28 Abr 2004||Uni-Charm Corporation||Water-disintegratable wiping sheet|
|EP0937453A3||25 Ene 1999||19 Abr 2000||Sam Schwartz||Cosmetic and tissue cleansing and moisturizing composition|
|EP0945536B1||18 Ene 1999||15 Oct 2008||Uni-Charm Corporation||Method of manufacturing a water disintegratable non-woven fabric and the water disintegratable non-woven fabric|
|EP1024225B1||28 Ene 2000||24 Mar 2004||Uni-Charm Corporation||Fibrillated rayon-containing, water-decomposable fibrous sheet|
|EP1039024B1||23 Mar 2000||25 Jun 2003||Uni-Charm Corporation||Water-decomposable non-woven fabric comprising regenerated cellulose fibers in different fiber lengths|
|EP1046747B1||19 Abr 2000||3 Nov 2010||Uni-Charm Corporation||Water-decomposable cleaning article and manufacturing method therefor|
|EP1050297A3||27 Abr 2000||15 Nov 2000||Fort James Corporation||Lotionized tissue products containing a pH balance compound for the skin|
|EP1065302B1||27 Dic 1999||13 Dic 2006||Pigeon Corporation||Wetness-responsive fiber, process for producing the same, nonwoven fabric, and use of these|
|FR2672788A1||Título no disponible|
|JP4943114B2||Título no disponible|
|JP6233809A||Título no disponible|
|1||Abstract Derwent WPI and JAPIO, JP 03-239709 (Lion Corp) Oct. 25, 1991.|
|2||Abstract Derwent WPI and JAPIO, JP 63/139906 (Lion Corp.) Jun. 11, 1988.|
|3||Abstract Derwent WPI, J: 1-306661 (Lion Corp) Dec. 11, 1989.|
|4||Abstract Derwent WPI, JP 5-179548 (Lion Corp), Jul. 20, 1993.|
|5||Abstract Derwent WPI, JP 62141199 (Agency of Ind Sci & Technology), Jun. 24, 1987.|
|6||Abstract Derwent WPI, JP 63 294851 (Takasago Perfumery Co), Dec. 1, 1988.|
|7||Carlsson et al., "Thermal Gelation of Nonionic Cellulose Ethers and Ionic Surfactants in Water", Colloids and Surfaces, vol. 47, pp. 147-165 (1990).|
|8||Chowdhury et al., "Direct Observation of the Gelatin of Rodlike Polymers", Poly. Mat. Sci. and Eng., vol. 59, pp. 1045-1052 (Sep., 1988).|
|9||D 5034-11, "Standard Test Method for Breaking Force and Elongation of Textile Fabrics (Grab Test)," 1994 Ann. Book of ASTM Standards, vol. 7.02, pp. 708-709 (1994).|
|10||Govindan, T.S., "Process for Making Smooth Vapro-Permeable Microporous Sheet Material", Defensive Publication, vol. T901 (007), (Aug. 1972).|
|11||Nagura et al., "Temperature-Viscosity Relationships of Aqueous Solutions of Cellulose Ethers", Kobunshi Ronbunshu, vol. 38, (3), pp. 133-137 (Aug. 1980).|
|12||Patent Abstract Japan, JP 06-207324 (Unitka Ltd.), Jul. 26, 1994.|
|13||Patent Abstract Japan, No. 01207457 (Uni-Charm Corp.), Aug. 21, 1989.|
|14||Patent Abstract Japan, No. 02082925 (Kinpou Seish KK), Mar. 23, 1990.|
|15||Patent Abstract Japan, No. 02221489 (Kanetoyo Seishi KK), Sep. 4, 1990.|
|16||Patent Abstract Japan, No. 03167400 (Nichirin Kagaku Kogyo KK), Jul. 19, 1991.|
|17||Patent Abstract Japan, No. 03213596 (S T Chem Co. Ltd Japan Vilene Co. Ltd), Sep. 18, 1991.|
|18||Patent Abstract Japan, No. 06192527 (Nichiyu Giken Kogyo KK), Jul. 12, 1994.|
|19||Patent Abstract Japan, No. 06207162 (S T Chem Co. Ltd.), Jul. 26, 1994.|
|20||Patent Abstract Japan, No. 09131388 (Kaminaga Taira), May 20, 1997.|
|21||Patent Abstract Japan, No. 09132896 (Uni Charm Corp.), May 20, 1997.|
|22||Patent Abstract Japan, No. 09132897 (Uni Charm Corp.), May 20, 1997.|
|23||Patent Abstract Japan, No. 10277088 (Kao Corp.), Oct. 20, 1998.|
|24||The Encyclopedia of Chemistry, 3rd Ed., p. 14, 1974.|
|Patente citante||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US7081139 *||25 Jul 2002||25 Jul 2006||E. I. Du Pont De Nemours And Company||Antimicrobial polyester-containing articles and process for their preparation|
|US7284930||20 Oct 2003||23 Oct 2007||Cjs Technology, Inc.||Composition and method for forming a sprayable materials cover|
|US7884037||15 Dic 2006||8 Feb 2011||Kimberly-Clark Worldwide, Inc.||Wet wipe having a stratified wetting composition therein and process for preparing same|
|US7892993||31 Ene 2006||22 Feb 2011||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US7902094||16 Ago 2005||8 Mar 2011||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8066956||15 Dic 2006||29 Nov 2011||Kimberly-Clark Worldwide, Inc.||Delivery of an odor control agent through the use of a presaturated wipe|
|US8148278||30 Dic 2010||3 Abr 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8158244||22 Dic 2010||17 Abr 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8163385||22 Dic 2010||24 Abr 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8178199||15 May 2012||Eastman Chemical Company||Nonwovens produced from multicomponent fibers|
|US8216953||13 Dic 2010||10 Jul 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8217219||10 Jul 2012||Kimberly-Clark Worldwide, Inc.||Anatomically conforming vaginal insert|
|US8227362||13 Dic 2010||24 Jul 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8236713||7 Ago 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8247335||21 Ago 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8257628||4 Sep 2012||Eastman Chemical Company||Process of making water-dispersible multicomponent fibers from sulfopolyesters|
|US8262958||11 Sep 2012||Eastman Chemical Company||Process of making woven articles comprising water-dispersible multicomponent fibers|
|US8273451||25 Sep 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8277706||2 Oct 2012||Eastman Chemical Company||Process of making water-dispersible multicomponent fibers from sulfopolyesters|
|US8314041||22 Dic 2010||20 Nov 2012||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8388877||5 Mar 2013||Eastman Chemical Company||Process of making water-dispersible multicomponent fibers from sulfopolyesters|
|US8398907||22 Dic 2010||19 Mar 2013||Eastman Chemical Company||Process of making water-dispersible multicomponent fibers from sulfopolyesters|
|US8435908||13 Dic 2010||7 May 2013||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8444895||21 May 2013||Eastman Chemical Company||Processes for making water-dispersible and multicomponent fibers from sulfopolyesters|
|US8444896||21 May 2013||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8506543||11 Jun 2012||13 Ago 2013||Kimberly-Clark Worldwide, Inc.||Anatomically conforming vaginal insert|
|US8512519||22 Abr 2010||20 Ago 2013||Eastman Chemical Company||Sulfopolyesters for paper strength and process|
|US8513147||27 Ago 2008||20 Ago 2013||Eastman Chemical Company||Nonwovens produced from multicomponent fibers|
|US8557374||22 Dic 2010||15 Oct 2013||Eastman Chemical Company||Water-dispersible and multicomponent fibers from sulfopolyesters|
|US8584685 *||21 Mar 2012||19 Nov 2013||Katherine Rose Kovarik||Nail polish remover method and device|
|US8623247||13 Dic 2010||7 Ene 2014||Eastman Chemical Company||Process of making water-dispersible multicomponent fibers from sulfopolyesters|
|US8691130||22 Dic 2010||8 Abr 2014||Eastman Chemical Company||Process of making water-dispersible multicomponent fibers from sulfopolyesters|
|US8757173||13 Nov 2013||24 Jun 2014||Katherine Rose Kovarik||Nail polish remover method and device|
|US8821687||9 Dic 2011||2 Sep 2014||H.B. Fuller Company||Flushable article including polyurethane binder and method of using the same|
|US8840757||28 Nov 2012||23 Sep 2014||Eastman Chemical Company||Processes to produce short cut microfibers|
|US8840758||28 Nov 2012||23 Sep 2014||Eastman Chemical Company||Processes to produce short cut microfibers|
|US8871052||28 Nov 2012||28 Oct 2014||Eastman Chemical Company||Processes to produce short cut microfibers|
|US8882963||28 Nov 2012||11 Nov 2014||Eastman Chemical Company||Processes to produce short cut microfibers|
|US8906200||28 Nov 2012||9 Dic 2014||Eastman Chemical Company||Processes to produce short cut microfibers|
|US8936030||18 Jun 2014||20 Ene 2015||Katherine Rose Kovarik||Nail polish remover method and device|
|US9005738||8 Dic 2011||14 Abr 2015||Buckeye Technologies Inc.||Dispersible nonwoven wipe material|
|US9121137||17 Abr 2014||1 Sep 2015||Sellars Absorbent Materials, Inc.||Dispersible articles and methods of making the same|
|US9175440||18 Sep 2014||3 Nov 2015||Eastman Chemical Company||Processes to produce short-cut microfibers|
|US9273417||14 Oct 2011||1 Mar 2016||Eastman Chemical Company||Wet-Laid process to produce a bound nonwoven article|
|US9303357||10 Abr 2014||5 Abr 2016||Eastman Chemical Company||Paper and nonwoven articles comprising synthetic microfiber binders|
|US9314142||3 Mar 2015||19 Abr 2016||Georgia-Pacific Nonwovens LLC||Dispersible nonwoven wipe material|
|US20030017194 *||25 Jul 2002||23 Ene 2003||Joerger Melissa C.||Antimicrobial polyester-containing articles and process for their preparation|
|US20050084334 *||20 Oct 2003||21 Abr 2005||Caijun Shi||Composition and method for forming a sprayable materials cover|
|US20050148995 *||29 Dic 2003||7 Jul 2005||Kimberly-Clark Worldwide, Inc.||Anatomically conforming vaginal insert|
|US20050209374 *||24 May 2004||22 Sep 2005||Matosky Andrew J||Anaerobically biodegradable polyesters|
|US20060147505 *||30 Dic 2004||6 Jul 2006||Tanzer Richard W||Water-dispersible wet wipe having mixed solvent wetting composition|
|US20060147689 *||30 Dic 2004||6 Jul 2006||Raj Wallajapet||Absorbent composites containing biodegradable reinforcing fibers|
|US20080145267 *||15 Dic 2006||19 Jun 2008||Kimberly-Clark Worldwide, Inc.||Delivery of an odor control agent through the use of a presaturated wipe|
|US20080145664 *||15 Dic 2006||19 Jun 2008||Kimberly-Clark Worldwide, Inc.||Wet wipe having a stratified wetting composition therein and process for preparing same|
|US20080196188 *||14 Jun 2006||21 Ago 2008||Kelheim Fibres Gmbh||Fibrous Composite that is Dissoluble or Decomposable in Water, and Products Manufactured Thereform|
|US20120240951 *||21 Mar 2012||27 Sep 2012||Katherine Rose Kovarik||Nail Polish Remover Method and Device|
|Clasificación de EE.UU.||525/221, 525/241, 525/222, 525/232|
|Clasificación internacional||A61L15/24, A47K10/32, A61F13/15, A61L15/62|
|Clasificación cooperativa||A61F13/15211, A61L15/62, A47K2010/3266, A61L15/24, Y10T428/249924, Y10T428/249933|
|Clasificación europea||A61L15/24, A61L15/62|
|24 Abr 2001||AS||Assignment|
Owner name: KIMBERLY-CLARK WORLDWIDE, INC., WISCONSIN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MUMICK, PAVNEET S.;CHEN, FRANKLIN M.C.;CHANG, YIHUA;REEL/FRAME:011745/0048;SIGNING DATES FROM 20010329 TO 20010415
|18 Dic 2006||FPAY||Fee payment|
Year of fee payment: 4
|7 Feb 2011||REMI||Maintenance fee reminder mailed|
|1 Jul 2011||LAPS||Lapse for failure to pay maintenance fees|
|23 Ago 2011||FP||Expired due to failure to pay maintenance fee|
Effective date: 20110701